Lecture1上海有机所课件.ppt

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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:tangy,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,C

2、hina,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 chan

3、ge 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

4、-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 198

5、7,109,6591-6600.,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 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 interactions,Shanghai,Ch

6、ina,-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,S

7、hanghai,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

8、,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 Eff

9、ects 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(be

10、tter 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

11、 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

12、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,C

13、hina,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 ar

14、ound 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 pro

15、cess;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 identify those FGs which will direct the reaction,H.Thopson JACS 1973,95,838.,烯烃的反应-基本反应,Shanghai,China,The first r

16、ational attempt to associate catalyst with substrate,H.Thopson JACS 1974,96,6232.,烯烃的反应-基本反应,Shanghai,China,Cationic Hydrogenation Catalysts,烯烃的反应-基本反应,Shanghai,China,Mechanism of Hydrogenation Cationic Rhodium-(I)Catalysts.,烯烃的反应-基本反应,Shanghai,China,Mechanism of Hydrogenation Cationic Rhodium-(I)Ca

17、talysts.,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,China,Polar 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

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

19、,1-6-1 Introduction,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,1-7 Olefin Oxymercuration-1,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,Chi

20、na,Shanghai,China,Shanghai,China,Shanghai,China,Problems of the day:,Shanghai,China,Shanghai,China,Shanghai,China,1-7 Related Olefin Addition Rxns:Halogen Electrophiles,Shanghai,China,Shanghai,China,Shanghai,China,Related Olefin Addition Rxns,Shanghai,China,Allenes:multi-reaction site chirality,Hydr

21、ohalogenation Reactions of Allenes,Shanghai,China,Ma et al.Pure&Appl.2001,73,337.,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,1-8 The Simmons-Smith Reaction,Shanghai,China,Shanghai,China,JACS,2003,12990.,Shanghai,China,Shanghai,China,1-9 Conjugate addition,烯烃的反应-基本反应,Michael,J.Prakt.

22、Chem.1887,35,349.Michael,Am.Chem.J.1887,9,115.,Shanghai,China,Case I,Case II,1-9-1 Introduction,Shanghai,China,Addition to a,b-unsaturated compounds:Organoalkali metal reagents from unstabilized carbanion:1,2-Enolate and other stabilized anion:1,4-Grignard reagents:1,2-(aldehyde),1,4-(Steric ones),1

23、,2-&1,4-mixtures(most cases)Organocopper reagents:1,4-Lithium diorganocopper reagents:1,4-Cu(I)-Grignard reagents:1,4-Other nucleophiles:,Shanghai,China,1-9-2 Stereochemistry,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Olefin Addition Rxns in Polyether Synthesis-1,Shanghai,China,Shanghai,China,