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1、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: ,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,Shan
2、ghai, 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,
3、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
4、),-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 sim
5、ilar 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)-
6、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: Hoffma
7、n, 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, C
8、hina,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
9、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 t
10、o 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
11、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-
12、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,
13、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
14、, 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,Th
15、ompson, 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
