Shanghai, China,有机合成反应,唐 勇 金属有机化学国家重点实验室,E-mail: tangymail.sioc.ac.cn,Shanghai, China,方法 考试,重要性,Shanghai, China, 中间体 产物的形成 官能团,简介,Shanghai, China,烯烃的反应-立体化学特性,Functional Group,Shanghai, China,烯烃的反应-立体化学特性,Shanghai, China,第一章 烯烃的反应,Shanghai, China,Representative Cis-Addition Processes,烯烃的反应-立体化学特性, 1-1 Introduction,Shanghai, China,烯烃的反应-立体化学特性,Shanghai, China,Representative Trans-Addition Processes,烯烃的反应-立体化学特性,Shanghai, China,烯烃的反应-立体化学特性,Shanghai, China,烯烃的反应-烯烃构象分析,D. Kim & Co-workers, Tetrahedron Lett. 1986, 27, 943., 1-2 Conformations of Olefinic Substrates,Shanghai, China,Propane versus Propene,烯烃的反应-烯烃构象分析,Hybridilzation change opens up the CCC bond angle,Shanghai, China,烯烃的反应-烯烃构象分析,Butane versus 1-Butene,Shanghai, China,1-butene,2-propen-1-ol,E (kcal/mol),-180 -90 0 (Deg) 90 180,5 4 3 2 1 0,Conforms to ab initio (3-21G) values: Wiberg, K. B.; Martin, E. J. Am. Chem. Soc. 1985, 107, 5035.,E (kcal/mol),-180 -90 0 (Deg) 90 180,5 4 3 2 1 0,烯烃的反应-烯烃构象分析,A-1,2 interactions,Shanghai, China,2-methyl-1-butene,2-methyl-2-propen-1-ol,E (kcal/mol),E (kcal/mol),5 4 3 2 1 0,5 4 3 2 1 0,-180 -90 0 (Deg) 90 180,-180 -90 0 (Deg) 90 180,烯烃的反应-烯烃构象分析,A-1,2 interactions,Shanghai, China,Acetaldehyde exhibits a similar conformational bias,烯烃的反应-烯烃构象分析,K. Houk, JACS 1987, 109, 6591-6600.,Shanghai, China,-180 -90 0 (Deg) 90 180,-180 -90 0 (Deg) 90 180,E (kcal/mol),E (kcal/mol),5 4 3 2 1 0,5 4 3 2 1 0,Values calculated using MM2 (molecular mechanics) force fields via the Macromodel multiconformation search.,(Z)-2-pentene (Z)-2-buten-1-ol,烯烃的反应-烯烃构象分析,A-1,3 interactions,Shanghai, China,-180 -90 0 (Deg) 90 180,5 4 3 2 1 0,E (kcal/mol),(Z)-2-hydroxy-3-pentene,The Torsional Energy Profile,烯烃的反应-烯烃构象分析,A-1,3 interactions,Shanghai, China,烯烃的反应-烯烃构象分析,A-1,3 interactions,Shanghai, China,烯烃的反应-烯烃构象分析,Review: Hoffman, R. W. Chem.Rev. 1989, 1841.,Shanghai, China,烯烃的反应-基本反应, 1-3 Olefin Hydroboration,Shanghai, China,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Represetative Hydroboration Examples: Acyclic Control,Shanghai, China,烯烃的反应-基本反应,Represetative Hydroboration Examples: Acyclic Control,Shanghai, China,烯烃的反应-基本反应,Represetative Hydroboration Examples: Cyclic Control,Shanghai, China, 1-4 Olefin Epoxidation,烯烃的反应-基本反应,Cis-selectivity,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China, Steric Effects How do we account for the high exo selectivities in addition reactions to norbornene?,Highly exo selective for electrophilic, nucleophilic and cycloaddition reactions Rate enhancement due to strain,Schleyer, P. R. J. Amer. Chem. Soc. 1967, 89, 701.,Addition from exo face avoids eclipsing A & B hydrogens (better hyperconjugative stabilization of transition state),烯烃的反应-基本反应,Shanghai, China, Associative Substrate-Reagent Interactions: directed reaction,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,Diastereoselective Peracid Epoxidation,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,The Sharpless Epoxidation,Shanghai, China,Epoxidation of Acyclic Alcohol,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,Epoxidation of Acyclic Homoallylic Alcohols,烯烃的反应-基本反应,Shanghai, China,Epoxidation of Acyclic Homoallylic Alcohols,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,New Methods,JACS 2000, 8317.,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,Science 2001, 1140,烯烃的反应-基本反应,Shanghai, China,Dioxirane Epoxidation,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Houk, JACS 1997, 12982.,Shanghai, China, 1-5 Olefin Hydrogenation,Relevant Review articles: Angew. Chem. Int. Edit. 26, 190-203 (1987).,Historically, primary stereochemical control designed around analysis of steric environment in vicinity of C=C.,烯烃的反应-基本反应,Shanghai, China,However, the influence of polar effects was documented,Thompson, J.Org. Chem. 36, 2577 (1971),烯烃的反应-基本反应,Shanghai, China,Polar functional groups may play a role in controlling the diastereoselectivity of the hydrogenation process; however, the control elements were not well-defined.,J. E. McMurry et al. Tetrahedron Lett 3731 (1970),烯烃的反应-基本反应,Shanghai, China,烯烃的反应-基本反应,Shanghai, China,The first rational attempt to identi