有机合成反应Lecture 1.pptVIP

方法 考试 However, the influence of polar effects was documented Thompson, J.Org. Chem. 36, 2577 (1971) 烯烃的反应-基本反应 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 烯烃的反应-基本反应 The first rational attempt to identify those FGs which will direct the reaction H. Thopson JACS 1973,95,838. 烯烃的反应-基本反应 The first rational attempt to associate catalyst with substrate H. Thopson JACS 1974,96,6232. 烯烃的反应-基本反应 Cationic Hydrogenation Catalysts 烯烃的反应-基本反应 Mechanism of Hydrogenation Cationic Rhodium-(I) Catalysts. 烯烃的反应-基本反应 Mechanism of Hydrogenation Cationic Rhodium-(I) Catalysts. That H atom lying parallel to the pi-system (HA) should migrate preferentiallyif the dihydride is an intermediate. 烯烃的反应-基本反应 烯烃的反应-基本反应 烯烃的反应-基本反应 Polar functional groups other than OH may also direct the process 烯烃的反应-基本反应 烯烃的反应-基本反应 烯烃的反应-基本反应 烯烃的反应-基本反应 烯烃的反应-基本反应 烯烃的反应-基本反应 烯烃的反应-基本反应 Homoallylic Alcohols Evans, Morrissey Tetrahedron Lett. 26 6005 (1985) § 1-6 Olefin Bromination-1 § 1-6-1 Introduction § 1-7 Olefin Oxymercuration-1 烯烃的反应-基本反应 Represetative Hydroboration Examples: Acyclic Control 烯烃的反应-基本反应 Represetative Hydroboration Examples: Cyclic Control § 1-4 Olefin Epoxidation 烯烃的反应-基本反应 Cis-selectivity 烯烃的反应-基本反应 烯烃的反应-基本反应 ? 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 ? Associative Substrate-Reagent Interactions: directed reaction 烯烃的反应-基本反应 烯烃的反应-基本反应 烯烃的反应-基本反应