Pd Catalyzed Coupling Reactions.ppt

Pd催化的偶联反应;常见配体 (Ligand) ;在M-X中X(配体)以满壳层离开时，金属所保留的电荷数，就是金属的氧化态。 ;过渡金属有机化合物的基元反应;配体的配位和解离;氧化加成;7;还原消除;插入和消除反应;烯烃的插入和b-H消除;Kumada, Negishi, Sonogashira, Stille, Suzuki, Hiyama, Buchwald, ; 偶联反应的机理 Mechanism of Cross-Coupling Reaction;13;J. Chatt and B. L. Shaw,? J. Chem. Soc. 1960, 1718-1729.;Preparation of Functionalized Arylmagnesium Reagents;V. Bonnet, F. Mongin, F. Trcourt, G. Quguiner, P. Knochel, Tetrahedron Lett. 2001, 42, 5717–5719.;Ruben Martin and Stephen L. Buchwald J. Am. Chem. Soc. 2007, 129, 3844-3845.;Stille 反应;19;Stille 反应条件;21;Preparation of Aryl and Vinyl Stannanes;23;24;25;26;27;Suzuki 反应;29;The typical order of reactivity of aryl electrophiles in palladium-catalyzed cross-couplings is I Br ≈ OTf Cl.;31;32;33;34;Preparation of Organoboron Compounds; 副反应 Side reactions;F. E. Goodson, T. I. Wallow, B. M. Novak, J. Am. Chem. Soc. 1997, 119, 12441-12453. F. E. Goodson, T. I. Wallow, B. M. Novak, Macromolecules 1998, 31, 2047-2056. V. V. Grushin, Organometallics 2000, 19, 1888-1900.;38; 氧气诱导的自身偶联 Oxygen-induced homocoupling; 脱卤 Dehalogenation; B-C键的水解断裂 Hydrolytic B-C bond cleavage;42;A. F. Littke, C. Dai, G. C. Fu, J. Am. Chem. Soc. 2000, 122, 4020-4028.;The unusual cross coupling activity furnished by P(t-Bu)3 may therefore be attributable both to its size and to its electron-richness: the steric demand favors dissociation (relative to less bulky phosphines) to a monophosphine complex that, due to the donating ability of P(t-Bu)3, readily undergoes oxidative addition.;A. F. Littke, C. Dai,G. C. Fu, J. Am. Chem. Soc. 2000, 122, 4020-4028.;46;47;48;49;50;51;Negishi偶联反应; 锌试剂的制备 Preparation of Zinc Organometallics;54;A. O. King, N. Yasuda Topics Organomet. Chem. 2004. 205-245; 钯催化的有机硅化合物和卤化物的偶联反应 Pd Catalyzed Cross-Coupling Reactions of Organosilicon Compounds with Halides;Yoshida, J., Tamao, K., Yamamoto, H., Kakui, T., Uchida, T., Kumada, M., Organometallics 1982, 1, 542-549. Hosomi, A., Kohra, S., Tominga, Y., Chem.