| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | May 28, 2002 |
| PATENT TITLE |
Ligands for metals and improved metal-catalyzed processes based thereon |
| PATENT ABSTRACT | One aspect of the present invention relates to novel, electron-rich bidentate ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject methods provide improvements in many features of the transition metal-catalyzed reactions, including the range of suitable substrates, reaction conditions, and efficiency |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | July 10, 1998 |
| PATENT REFERENCES CITED |
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VI. .sup.1,2) Asymmetric Synthesis of a Cyclopentene Derivative by Transition Metal-Catalyzed Asymmetric Vinylcyclopropane-Cyclopentene Rearrangements with Chiral Phosphine Ligands," Chem. Pharm. Bull., 42(3) pp. 470-474 1994. Shirakawa, E., et al, "Carbostannylation of Alkynes Catalized by an Iminophosphine--Palladium Complex," J. Am. Chem. Soc., 120, pp. 2975-2976, 1998. Sodeoka, M., et al., Stable Diaqua Palladium (II) Complexes of BINAP and Tol-BINAP as Highly Efficient Catalysts for Asymmetric Aldol Reactions, SYNLETT, pp. 463-466, May 1997. Sodeoka, M., et al., "Asymmetric Synthesis Using Palladium Catalysts," Pure & Appl. Chem., vol. 70, No. 2, pp. 411-414, 1998. Tamao, K., et al., "Optically Active 2,2'-bis(Diphenylphosphinomethyl)-1,1'-Binaphthyl: A New Chiral Bidentate Phosphine Ligand for Transition-Metal Complex Catalyzed Asymmetric Reactions," Tetrahedron Letters, No. 16, pp. 1389-1392, 1977. 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B. et al., "Coupling of a Heteroaryl Chlorides tieh Arylboronic Acids in the Presence of [1,4-Bis-(Diphenylphosphine)Butane]Palladium(II) Dichloride", Tetrahedron Letters, 20:273-2276 (1991). Muratake, H. et al., "Intramolecular Cyclization Using Palladium-Catalyzed Arylation toward Formyl and Nitro Groups", Tetrahedron Letters, 40:2355-2358 (1999). Muratake, H. et al., "Palladium-Catalyzed Intramolecular .alpha.-Arylation of Aliphatic Ketones", Tetrahedron Letters, 38:7581-7582 (1997). Nishiyama, M. et al., "Synthesis of N-Arylpiperazines from Aryl Halides and Piperazine under a Palladium Tri-tert-butylphosphine Catalyst", Tetrahedron Letters, 39:617-620 (1998). Reddy, N. P. et al., "Palladium-Catalyzed Amination of Aryl Chlorides", Tetrahedron Letters, 27:4807-4810 (1997). Reirmeier, T. et al., "Palladium-catalyzed C-C- and C-N-coupling reactions of Aryl Chlorides", Topics in Catalysis, 4:301-309 (1997). Saito, S. et al., "Synthesis of Biaryls via a Nickle(0)-Catalyzed Cross Coupling Reaction of Chloroarenes with Arylboronic Acids", J. Org. Chem., 62:8024-8030 (1997). Shen, W., "Palladium Catalyzed Coupling of Aryl Chlorides with Arylboronic Acids", Tetrahedron Letters, 38:5575-5578 (1997). Thompson, W. et al., "An Efficient Synthesis of Arylpyrazines and Bipyridines", J. Org. Chem., 53:2052-2055 (1988). Uemura, M. et al., "Catalytic asymmetric induction of planar chirality: Palladium-catalyzed asymmetric cross-coupling of meso tricarconyl(arene)chromium complexes with alkenyl- and arylboronic acids", J. Organometallic Chem., 473:129-137 (1994). Wang, D. et al., "New polymerization catalyzed by palladium complexes: synthesis of poly(p-phenylenevinylene) derivatives", Chem. Commun., 529-530 (1999). Yamamoto, T. et al., "Palladium-Catalyzed Synthesis of Triarylamines from Aryl Halides and Diarylamines", Tetrahedron Letters, 39:2367-2370 (1998). Aranyos et al., "Novel Electron-Rich Bulky Phosphine Ligands Facilitate the Palladium-Catalyzed Preparation of Diaryl Ethers", J. Am. Chem. Soc. 121:4369-4378 (1999). Bronco, S. and Consiglio, G., "Regio- and Stereoregular Copolymerisation of Propene with Carbon Monoxide, Catalysed by Palladium Complexes Containing Atropisomeric Diphosphine Ligands", Macromol. Chem. Phys. 197:355-365 (1996). Chemical Abstracts vol. 123; No. 15, Oct. 9, 1995, Abstract No. 197945; Columbus, Ohio, US. Chemical Abstracts vol. 124 No. 25, Jun. 17, 1996; Abstract No. 343650, Columbus Ohio, US. Chemical Abstracts vol. 127 No. 21; Nov. 24, 1997, Abstract No. 293410, Columbus Ohio. Cho, Y. S. and Shibasaki, M.; "Synthesis and Evaluation of a New Chiral Ligand: 2-diphenylarsino-2'-diphenylphosphino-1, 1'-binaphthyl (BINAPAS)", Tetrahedron Letters 39 : 1733-1776 (1998). Crameri et al., "Pratical Synthesis of (S)-2-(4-fluorophenyl)-3-methylbutanoic acid, key building block for the calcium antagonist Mibefradil", Tetrahedron : Asymmetry 8 (21): 3617-3623 (1997). Ding, K. et al., "Highly Efficient and Pratical Optical Resolution of 2-Amino-2'-hydroxy-1, 1'-binaphthyl by Molecular Complexation with N-Benzylcinchonidium Chloride: A Direct Transformation to Binaphthyl Amino Phosphine", Chem. Eur. J. 5 (6):1734-1737 (1999). Empsall, D. H. et al., "Complexes of Platinum and Paladium with Tertiary Dimethoxyphenyl-Phosphines: Attempts to Effect O- or C-Metallation", Journal of the Chemical Society Dalton Transactions No. 3 : 257-262 (1978). Gill, F. D. et al., "Transition Metal-Carbon Bonds. Part XXXIII..sup.1 Internal Metallations of Secondary and Tertiary Carbon Atoms by Platinum(II) and Palladium (II).", Journal of the Chemical Society, Dalton Transactions No. 3: 270-278 (1973). Gladiali, S. et al., "Synthesis, Crystal Structure, Dynamic Behavior and Reactivity of Dinaphthol (2,1-b:1',2'-diphospholes and Related Atropisomeric Phosphacyclic Derivatives", J. Org. Chem. 59 (21): 6363-6371 (Oct. 21, 1994). Gladiali, S. et al., "Novel Heterobidentate Ligands for Asymmetric Catalysis: Synthesis and Rhodium-catalyzed Reactions of S-Alkyl (R)-2-Diphenylphosphino-1, 1'-binaphthyl-2'-thiol", Tetrahedron: Asymmetry 5 (7): 1143-1146 (1994). Hayashi Tamion, "Asymmetric Hydrosilylation of Olefins Catalyzed by MOP-Platinum Complexes", Acta Chem. Scand. 50 (3): 259-266 (1996). Hattori, T. et al., "Nucleophilic Aromatic Substitution Reactions of 1- Methoxy-2-(diphenylphosphinyl)naphthalene with C-, N-, and O-Nucleophiles: Facile Synthesis of Diphenyl(1-substituted-2-naphthyl)Phosphines", Synthesis, No. 2 : 199-202 (Feb. 1994). Herrmann, A. et al.,"Palladacycles: Efficient New Catalysts for the Heck Vinylation of Aryl Halides", Chemistry, A European Journal, 3 (8) :1357-1364 (Aug. 1997). Langer et al., "Catalytic Asymmetric Hydrosilylation of Ketones Using Rhodium-(I)-Complexes of Chiral Phosphinooxazoline Ligands", Tetrahedron : Asymmetry 7(6): 1599-1602 (1996). Jones et al., "O- and C- Metallation of 2-Alkoxyphenylphosphines by Platinum (II)", Journal of the Chemical Society, Dalton Transactions, No. 9 : 992-999 (1974). Old, W. et al., "A Highly Active Catalyst for Palladium-Catalyzed Cross-Coupling Reactions: Room-Temperature Suzuki Couplings and Amination of Unactivated Aryl Chlorides", J. Am. Chem. Soc. 120: 9722-9723 (1998). Palucki et al., "Synthesis of Oxygen Heterocycles via a Palladium Catalyzed C-O Bond Forming Reaction", J. Am. Chem. Soc. 118: 10333-10334 (1996). Palucki et al., "Palladium-Catalyzed Intermolecular Carbon-Oxygen Bond Formation: A New Synthesis of Aryl Ethers", J. Am. Chem. Soc. 119 : 3395-3396 (1997). Vyskocil et al., "Derivatives of 2-Amino-2'-dephenylphosphino-1, 1'-binaphthyl (MAP) and Their Application in Asymmetric Palladium(O)-Catalyzed Allylic Substitution", J. Org. Chem. 63 (22) : 7738-7748 (1998). Wolfe, P. J. and Buchwald, L. S. "A Highly Active Catalyst for the Room-Temperature Amination and Suzuki Coupling of Aryl Chlorides", Angewandte Chemie, International Edition 38 (16) : 2413-2416 (1999). Wolfe, P. J. et al. "Highly Active Palladium Catalysts for Suzuki Coupling Reactions", J. Am. Chem. Soc. 121(41):9550-9561 (Oct. 20, 1999). |
| PATENT GOVERNMENT INTERESTS |
GOVERNMENT SUPPORT This invention was made with government support under Grant Number 9421982-CHE awarded by the National Science Foundation. The government has certain rights in the invention |
| PATENT CLAIMS |
We claim: 1. The ligand represented by structure 4: ##STR114## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, one, two, three, or four times; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycycle; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is a mixture of enantiomers or a single enantiomer. 2. The ligand of claim 1, wherein: R.sub.1 and R.sub.2 are absent; both instances of R in N(R).sub.2 are lower alkyl; and both instances of R in P(R).sub.2 are cycloalkyl. 3. The ligand represented by structure 7: ##STR115## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the four aryl rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is a mixture of enantiomers or a single enantiomer. 4. The ligand of claim 3, wherein: R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are absent; both instances of R in N(R).sub.2 are lower alkyl; and both instances of R in P(R).sub.2 are cycloalkyl. 5. The method depicted in Scheme 1: ##STR116## wherein Ar is selected from the group consisting of unsubstituted and substituted monocyclic and polycyclic aromatic and heteroaromatic moieties; X is selected from the group consisting of Cl, Br, I, --OS(O).sub.2 alkyl, and --OS(O).sub.2 aryl; R' and R" are selected, independently for each occurrence, from the group consisting of H, alkyl, aryl, heteroaryl, aralkyl, alkoxyl, amino, trialkylsilyl, and triarylsilyl; or R' and R", taken together, form an unsubstituted or substituted ring having 3-10 backbone atoms inclusive; said ring, having zero, one or two heteroatoms in its backbone; or R' or R" or both are covalently linked to Ar; the transition metal is selected from the group consisting of the Group VIIIA metals; the base is selected from the group consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions; the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive: ##STR117## wherein A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms; X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, tbioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; A and B independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR118## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, taken together, represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR119## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; the B and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR120## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80, the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR121## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR122## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR123## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer. 6. The method of claim 5, wherein the ligand of the present invention is structure 4; the transition metal is palladium; and the base is an alkoxide, amide, phosphate, or carbonate. 7. The method of claim 6, wherein the ligand of the present invention is structure 4, wherein R.sub.1 and R.sub.2 are absent; P(R).sub.2 represents PCy.sub.2, and N(R).sub.2 represents NMe.sub.2 ; and X represents Cl or Br. 8. The method of claim 7, wherein: HN(R')R" represents an unsubstituted or substituted heteroaromatic compound. 9. The method of claim 5, wherein: X represents Cl; the ligand of the present invention is structure 4, wherein R.sub.1 and R.sub.2 are absent, P(R).sub.2 represents PCy.sub.2, and N(R).sub.2 represents NMe.sub.2 ; the transition metal is palladium; and the base is an alkoxide, amide, phosphate, or carbonate. 10. The method of claim 5, wherein: X represents Br or I; the ligand of the present invention is structure 4, wherein R.sub.1 and R.sub.2 are absent, P(R).sub.2 represents PCy.sub.2, and N(R).sub.2 represents NMe.sub.2 ; the transition metal is palladium; the base is an alkoxide, amide, phosphate, or carbonate; and the method is practiced at room temperature. 11. The method of claim 5, wherein: X represents Cl; the ligand of the present invention is structure 5, wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are absent, and all occurrences of R are cyclohexyl; the transition metal is palladium; and the base is an alkoxide, amide, phosphate, or carbonate. 12. The method of claim 5, wherein: X represents Cl; the ligand of the present invention is structure 2, wherein X and Y both represent P, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are absent, and all occurrences of R are cyclohexyl; the transition metal is palladium; and the base is an alkoxide, amide, phosphate, or carbonate. 13. The method of claim 5, 6, 7, 8, 9, 10, 11, or 12, wherein the yield of ArN(R')R" is greater than 50%. 14. The method of claim 5, 6, 7, 8, 9, 10, 11, or 12, wherein the yield of ArN(R')R" is greater than 70%. 15. The method of claim 5, 6, 7, 8, 9, 10, 11, or 12, wherein the yield of ArN(R')R" is greater than 85%. 16. The method depicted in Scheme 2: ##STR124## wherein Ar and Ar' are independently selected from the group consisting of unsubstituted and substituted monocyclic and polycyclic aromatic and heteroaromatic moieties; X is selected from the group consisting of Cl, Br, I, --OS(O).sub.2 alkyl, and --OS(O).sub.2 aryl; the transition metal is selected from the group consisting of the Group VIIIA metals; the base is selected from the group consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions; the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive: ##STR125## wherein A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms; X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; A and B independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR126## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, taken together, represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR127## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or R.sub.1, and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; the B and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR128## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR129## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR130## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR131## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer. 17. The method of claim 16, wherein the transition metal is palladium; the ligand of the present invention is structure 4; and the base is an alkoxide, amide, carbonate, phosphate, or fluoride. 18. The method of claim 17, wherein the ligand of the present invention is structure 4, wherein R.sub.1 and R.sub.2 are absent; P(R).sub.2 represents PCy.sub.2, and N(R).sub.2 represents NMe.sub.2 ; X represents Cl or Br; and the method is practiced at room temperature. 19. The method of claim 16, 17, or 18, wherein the yield of Ar-Ar' is greater than 50%. 20. The method of claim 16, 17, or 18, wherein the yield of Ar-Ar' is greater than 70%. 21. The method of claim 16, 17, or 18, wherein the yield of Ar-Ar' is greater than 85%. 22. The method depicted in Scheme 3: ##STR132## wherein Ar is selected from the group consisting of unsubstituted and substituted monocyclic and polycyclic aromatic and heteroaromatic moieties; R is selected from the group consisting of alkyl, and aralkyl; R' is selected, independently for each occurrence, from the group consisting of alkyl, wherein the two B-R' bonds are inert under the reaction conditions; X is selected from the group consisting of Cl, Br, I, --OS(O).sub.2 alkyl, and --OS(O).sub.2 aryl; the transition metal is selected from the group consisting of the Group VIIIA metals; the base is selected from the group consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions; the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive: ##STR133## wherein A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms; X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; A and B independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heterdatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR134## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.1, R.sub.7, and R.sub.8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, taken together, represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR135## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; the B and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR136## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR137## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR138## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR139## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer. 23. The method of claim 22, wherein X represents Cl or Br; the transition metal is palladium; the ligand of the present invention is structure 4; and the base is an alkoxide, amide, carbonate, phosphate, or fluoride. 24. The method of claim 23, wherein the ligand of the present invention is structure 4, wherein R.sub.1 and R.sub.2 are absent; P(R).sub.2 represents PCy.sub.2, and N(R).sub.2 represents NMe.sub.2 ; and X represents Cl. 25. The method of claim 22, 23, or 24, wherein the yield of Ar-R is greater than 50%. 26. The method of claim 22, 23, or 24, wherein the yield of Ar-R is greater than 70%. 27. The method of claim 22, 23, or 24, wherein the yield of Ar-R is greater than 85%. 28. The method depicted in Scheme 4: ##STR140## wherein Ar is selected from the group consisting of unsunstituted and substituted monocyclic and polycyclic aromatic and heteroaromatic moieties; R, R', and R" are selected, independently for each occurrence, from the group consisting of H, alkyl, aralkyl, aryl, and heteroaryl; X is selected from the group consisting of Cl, Br, I, --OS(O).sub.2 alkyl, and --OS(O).sub.2 aryl; the transition metal is selected from the group consisting of the Group VIIIA metals; the base is selected from the group consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions; the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive: ##STR141## wherein A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms; X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioakyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; A and B independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR142## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, taken together, represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR143## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; the B and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR144## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR145## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR146## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR147## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer. 29. The method of claim 28, wherein X represents Cl or Br; the transition metal is palladium; the ligand of the present invention is structure 4; and the base is an alkoxide, or amide. 30. The method of claim 29, wherein the ligand of the present invention is structure 4, wherein R.sub.1 and R.sub.2 are absent; P(R).sub.2 represents PCy.sub.2, and N(R).sub.2 represents NMe.sub.2. 31. The method of claim 30, wherein X represents Br; and the method is practiced at room temperature. 32. The method of claim 28, 29, 30, or 31, wherein the yield of the product is greater than 50%. 33. The method of claim 28, 29, 30, or 31, wherein the yield of the product is greater than 70%. 34. The method of claim 28, 29, 30, or 31, wherein the yield of the product is greater than 85%. 35. The method depicted in Scheme 5: ##STR148## wherein alkenyl is selected from the group consisting of unsubstituted and substituted alkenyl moieties; X is selected from the group consisting of Cl, Br, I, --OS(O).sub.2 alkyl, and --OS(O).sub.2 aryl; R' and R" are selected, independently for each occurrence, from the group consisting of H, alkyl, aryl, heteroaryl, aralkyl, alkoxyl, amino, trialkylsilyl, and triarylsilyl; or R' and R", taken together, form an unsubstituted or substituted ring having 3-10 backbone atoms inclusive; said ring having zero, one or two heteroatoms in its backbone; the transition metal is selected from the group consisting of the Group VIIIA metals; the base is selected from the group consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions; the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive: ##STR149## wherein A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms; X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; A and B independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR150## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, taken together, represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR151## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; the B and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR152## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR153## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR154## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR155## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer. 36. The method depicted in Scheme 6: ##STR156## wherein Y and Z are independently selected from the group consisting of unsubstituted and substituted alkenyl, monocyclic and polycyclic aromatic and heteroaromatic moieties, wherein Y or Z or both represents alkenyl; X is selected from the group consisting of Cl, Br, I, --OS(O).sub.2 alkyl, and --OS(O).sub.2 aryl; the transition metal is selected from the group consisting of the Group VIIIA metals; the base is selected from the group consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions; the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive: ##STR157## wherein A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms; X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; A and B independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together optionally Represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR158## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, taken together, represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR159## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbarnate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; the B and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR160## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR161## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR162## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR163## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer. 37. The method depicted in Scheme 7: ##STR164## wherein alkenyl is selected from the group consisting of unsubstituted and substituted alkenyl moieties; R is selected from the group consisting of alkyl, and aralkyl; R' is selected, independently for each occurrence, from the group consisting of alkyl; wherein the two B-R' bonds are inert under the reaction conditions; X is selected from the group consisting of Cl, Br, I, --OS(O).sub.2 alkyl, and --OS(O).sub.2 aryl; the transition metal is selected from the group consisting of the Group VIIIA metals; the base is selected from the group consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions; the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive: ##STR165## wherein A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms; X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; A and B independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR166## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, taken together, represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR167## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; the B and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR168## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR169## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR170## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR171## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer. 38. The method depicted in Scheme 8: ##STR172## wherein alkenyl is selected from the group consisting of unsubstituted and substituted alkenyl moieties; R, R', and R" are selected, independently for each occurrence, from the group consisting of H, alkyl, aralkyl, aryl, and heteroaryl; X is selected from the group consisting of Cl, Br, I, --OS(O).sub.2 alkyl, and --OS(O).sub.2 aryl; the transition metal is selected from the group consisting of the Group VIIIA metals; the base is selected from the group consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions; the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive: ##STR173## wherein A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms; X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate,,phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; A and B independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR174## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, R.sub.4, Rs, R.sub.6, R.sub.7, and R.sub.8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8, taken together, represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR175## wherein X and Y represent, independently for each occurrence, N, P, As, OR, or SR; R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; or R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring; said ring having zero, one or two heteroatoms in its backbone; and said ring is substituted or unsubstituted; R.sub.5 and R.sub.6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or --(CH.sub.2).sub.m --R.sub.80 ; the B and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.5 and R.sub.6, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR176## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR177## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR178## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A and A' rings of the biphenyl core independently are unsubstituted or substituted with R.sub.1 and R.sub.2, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1 and R.sub.2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and ligand, when chiral, is mixture of enantiomers or a single enantiomer; ##STR179## wherein R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and --(CH.sub.2).sub.m --R.sub.80 ; the A, B, A', and B' rings of the binaphthyl core independently are unsubstituted or substituted with R.sub.1, R.sub.2, R.sub.3, and R.sub.4, respectively, any number of times up to the limitations imposed by stability and the rules of valence; R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, --SiR.sub.3, and --(CH.sub.2).sub.m --R.sub.80 ; R.sub.80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl; m is independently for each occurrence an integer in the range 0 to 8 inclusive; and the ligand, when chiral, is mixture of enantiomers or a single enantiomer. 39. The method of claim 35, 36, 37, or 38, wherein the yield of the product is greater than 50%. 40. The method of claim 35, 36, 37, or 38, wherein the yield of the product is greater than 70%. 41. The method of claim 35, 36, 37, or 38, wherein the yield of the product is greater than 85%. 42. The ligand of claim 1 or 3, wherein said ligand is covalently linked to a polymeric support or solid support. 43. The method of claim 5, 4, 22, 28, 35, 36, 37, or 38, wherein said ligand of the present invention is covalently linked to a polymeric support or a solid support |
| PATENT DESCRIPTION |
BACKGROUND OF THE INVENTION Transition metal catalyst complexes play important roles in many areas of chemistry, including the preparation of polymers and pharmaceuticals. The properties of these catalyst complexes are recognized to be influenced by both the characteristics of the metal and those of the ligands associated with the metal atom. For example, structural features of the ligands can influence reaction rate, regioselectivity, and stereoselectivity. Bulky ligands can be expected to slow reaction rate; electron-withdrawing ligands, in coupling reactions, can be expected to slow oxidative addition to, and speed reductive elimination from, the metal center; and electron-rich ligands, in coupling reactions, conversely, can be expected to speed oxidative addition to, and slow reductive elimination from, the metal center. In many cases, the oxidative addition step in the accepted mechanism of a coupling reaction is deemed to be rate limiting. Therefore, adjustments to the catalytic system as a whole that increase the rate of the oxidative addition step should increase overall reaction rate. Additionally, the rate of oxidative addition of a transtion metal catalyst to the carbon-halogen bond of an aryl halide is known to decrease as the halide is varied from iodide to bromide to chloride, all other factors being equal. Because of this fact, the more stable, lower molecular weight, and arguably more easy to obtain, members of the set of reactive organic halides--the chlorides--are the poorest substrates for transition metal catalyzed coupling reactions and the like. To date, the best halogen-containing substrates for transtion metal catalyzed carbon-heteroatom and carbon-carbon bond forming reactions have been the iodides. Bromides are often acceptable substrates, but typically required higher temperatures, longer reaction times, and give lower yields of products. Catalyst systems that possess greater substrate flexibility, e.g., the ability to utilize organic chlorides, and/or that produce the desired products efficiently and rapidly at lower temperatures, e.g. less than about 50.degree. C. or at room temperature, are not well precedented. SUMMARY OF THE INVENTION One aspect of the present invention relates to novel, electron-rich bidentate ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject methods provide improvements in many features of the transition metal-catalyzed reactions, including the range of suitable substrates, reaction conditions, and efficiency. Unexpected improvements over the prior art have been realized in transition metal-catalyzed: aryl amination reactions; Suzuki couplings to give both biaryl and alkylaryl products; and .alpha.-arylations of ketones. The ligands and methods of the present invention enable for the first time, the efficient use of aryl chlorides, inter alia, in the aforementioned reactions. Additionally, the ligands and methods of the present invention enable for the first time a subset of these transformations, e.g., with aryl bromides, to proceed efficiently at room temperature. |
| PATENT EXAMPLES | available on request |
| PATENT PHOTOCOPY | available on request |
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