【上海有机所】-有机合成课件

1、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 GroupShanghai, China烯烃的反应-立体化学特性Shanghai, China第一章 烯烃的反应Shanghai, ChinaRepresentative Cis-Addition Processes烯烃的反应-立体化学特性 1-1 IntroductionShanghai, China烯烃的反应-立体化学特性Shanghai, Ch

2、inaRepresentative 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 SubstratesShanghai, ChinaPropane versus Propene烯烃的反应-烯烃构象分析Hybridilzation change opens up the CCC bond angle

3、Shanghai, China烯烃的反应-烯烃构象分析Butane versus 1-ButeneShanghai, China1-butene2-propen-1-olE (kcal/mol)-180 -90 0 (Deg) 90 1805 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 1805 4 3 2 1 0烯烃的反应-烯烃构象分析A-1,2 interac

4、tionsShanghai, China2-methyl-1-butene2-methyl-2-propen-1-olE (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 interactionsShanghai, ChinaAcetaldehyde exhibits a similar conformational bias烯烃的反应-烯烃构象分析K. Houk, JACS 1987, 109, 6591-6600.Shang

5、hai, China-180 -90 0 (Deg) 90 180-180 -90 0 (Deg) 90 180E (kcal/mol)E (kcal/mol)5 4 3 2 1 05 4 3 2 1 0Values calculated using MM2 (molecular mechanics) force fieldsvia 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 interactionsShanghai, China-180 -90 0 (Deg)

6、90 1805 4 3 2 1 0E (kcal/mol)(Z)-2-hydroxy-3-penteneThe Torsional Energy Profile烯烃的反应-烯烃构象分析A-1,3 interactionsShanghai, China烯烃的反应-烯烃构象分析A-1,3 interactionsShanghai, 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 HydroborationShanghai, ChinaShanghai,

7、 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 ControlShanghai, China烯烃的反应-基本

8、反应 Represetative Hydroboration Examples: Acyclic ControlShanghai, China烯烃的反应-基本反应 Represetative Hydroboration Examples: Cyclic ControlShanghai, China 1-4 Olefin Epoxidation烯烃的反应-基本反应 Cis-selectivityShanghai, 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 f

9、or the high exo selectivities in addition reactions to norbornene? Highly exo selective for electrophilic, nucleophilic and cycloaddition reactions Rate enhancement due to strainSchleyer, P. R. J. Amer. Chem. Soc. 1967, 89, 701.Addition from exo face avoids eclipsing A & B hydrogens (better hypercon

10、jugative 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, ChinaDiastereoselective Peracid Epoxidation烯

11、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, ChinaThe Sharpless EpoxidationShanghai, ChinaEpoxidation of Acyclic Alcohol烯烃的反应-基本反应 Shanghai, China烯烃的反应-基本反应 Shanghai, ChinaEpoxidation of Acyclic Homoallylic Alcohols烯烃的反应-基本反应 Shanghai, ChinaEpoxidation of Acyclic Homoallyl

12、ic 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, ChinaNew MethodsJACS 2000, 8317.烯烃的反应-基本反应 Shanghai, China烯烃的反应-基本反应 Shanghai, ChinaScience 2001, 1140烯烃的反应-基本反应 Shanghai, ChinaDioxirane 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 Shan

13、ghai, 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 HydrogenationRelevant Review articles: Angew. Chem. Int. Edit. 26, 190-203 (1987).Historically, primary stereochemical control designed around analysi

14、s of steric environment in vicinity of C=C.烯烃的反应-基本反应 Shanghai, ChinaHowever, the influence of polar effects was documentedThompson, J.Org. Chem. 36, 2577 (1971)烯烃的反应-基本反应 Shanghai, ChinaPolar functional groups may play a role in controlling the diastereoselectivity of the hydrogenation process; how

15、ever, 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, ChinaThe first rational attempt to identify those FGs which will direct the reactionH. Thopson JACS 1973,95,838.烯烃的反应-基本反应 Shanghai, ChinaThe first ration

16、al attempt to associate catalyst with substrateH. Thopson JACS 1974,96,6232.烯烃的反应-基本反应 Shanghai, ChinaCationic Hydrogenation Catalysts烯烃的反应-基本反应 Shanghai, ChinaMechanism of Hydrogenation Cationic Rhodium-(I) Catalysts.烯烃的反应-基本反应 Shanghai, ChinaMechanism of Hydrogenation Cationic Rhodium-(I) Catalyst

17、s.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 Shanghai, China烯烃的反应-基本反应 Shanghai, China烯烃的反应-基本反应 Shanghai, ChinaPolar functional groups other than OH may also direct the process烯烃的反应-基本反应 Shanghai, China烯烃的反应-基本反应 Shan

18、ghai, 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, ChinaHomoallylic Alcohols Evans, Morrissey Tetrahedron Lett. 26 6005 (1985)Shanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, China 1-6 Olefin Bromination-1 1-6

19、-1 IntroductionShanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, China 1-7 Olefin Oxymercuration-1Shanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, ChinaSh

20、anghai, ChinaShanghai, ChinaShanghai, ChinaProblems of the day:Shanghai, ChinaShanghai, ChinaShanghai, China 1-7 Related Olefin Addition Rxns: Halogen ElectrophilesShanghai, ChinaShanghai, ChinaShanghai, ChinaRelated Olefin Addition RxnsShanghai, ChinaAllenes: multi-reaction site chiralityHydrohalogenation Reactions of AllenesShanghai, ChinaMa et al. Pure & Appl. 2001, 73, 337.Shanghai, ChinaShanghai, ChinaShanghai, ChinaShanghai, China 1-8 The Simmons-Smith ReactionShanghai, ChinaShanghai, ChinaJACS, 2003, 12990.Shanghai, ChinaShanghai, China 1-9 Conjugate addition烯烃的反应-基本反应