有机所唐勇讲义-2.pptVIP

§ 1-7 Olefin Oxymercuration-1 Problems of the day: § 1-7 Related Olefin Addition Rxns: Halogen Electrophiles Related Olefin Addition Rxns Allenes: multi-reaction site chirality Hydrohalogenation Reactions of Allenes Ma et al. Pure Appl. 2001, 73, 337. § 1-8 The Simmons-Smith Reaction Shanghai, China 有机合成反应 唐 勇 金属有机化学国家重点实验室 § 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 § 1-5-1 The influence of polar effects-Pd 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 § 1-5-2 The influence of polar effects-Cationic Catalysts 烯烃的反应-基本反应 H. Thopson JACS 1974,96,6232. 烯烃的反应-基本反应 The first rational attempt to associate catalyst with substrate 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 Furst-Plattner Rule: A rigid cyclohexene oxide system: those stereoelectronic effects that operate in ring cleavage also influence ring formation. Shanghai, China * * * * MX time (h) product yield (%) NaI 25 a 89 LiBra 48 b 90 LiCla 48 c 96 a LiX monohyd