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1、RHODIUMCATALYZEDHYDROFORMYLATIONCatalysisbyMetalComplexesVolume22Editors:B.R.James,TheUniversityofBritishColumbia,Vancouver,CanadaP.W.N.M.vanLeeuwen,UniversityofAmsterdam,TheNetherlandsAdvisoryBoard:I.Horváth,ExxonCorporateResearchLaboratory,Annandale,NJ,U.S.A.
2、S.D.Ittel,E.I.duPontdeNemoursCo.,Inc.,Wilmington,Del.,U.S.A.A.Nakamura,OsakaUniversity,Osaka,JapanW.H.Orme-Johnson,M.I.T,Cambridge,Mass.,U.S.A.R.L.Richards,JohnInnesCentre,Norwich,U.K.A.Yamamoto,WasedaUniversity,Tokyo,JapanThetitlespublishedinthisseriesareliste
3、dattheendofthisvolume.RHODIUMCATALYZEDHYDROFORMYLATIONEditedbyPIETW.N.M.VANLEEUWENInstituteofMolecularChemistry,UniversityofAmsterdam,Amsterdam,TheNetherlandsandCARMENCLAVERDepartmentdeQuimicaFísicaiInorgánica,UniversitatRoviraiVirgili,Tarragona,SpainKLUWERACAD
4、EMICPUBLISHERSNEWYORK/BOSTON/DORDRECHT/LONDON/MOSCOWeBookISBN:0-306-46947-2PrintISBN:0-792-36551-8©2002KluwerAcademicPublishersNewYork,Boston,Dordrecht,London,MoscowAllrightsreservedNopartofthiseBookmaybereproducedortransmittedinanyformorbyanymeans,electronic,m
5、echanical,recording,orotherwise,withoutwrittenconsentfromthePublisherCreatedintheUnitedStatesofAmericaVisitKluwerOnlineat:http://www.kluweronline.comandKluwer'seBookstoreat:http://www.ebooks.kluweronline.comTABLEOFCONTENTSPrefacexi1Introductiontohydroformylatio
6、n1PietW.N.M.vanLeeuwen1.1Historyofphosphorusligandeffects11.2Hydroformylation61.3Ligandparameters82Hydroformylationwithunmodifiedrhodiumcatalysts15RaffaelloLazzaroni,RobertaSettamboloandAldoCaiazzo2.1Introduction152.2Regioselectivityintherhodium-catalyzedhydrof
7、ormylationofvinylandvinylidenicsubstrates162.2.1Catalystprecursors172.2.2Influenceofthealkenestructureontheregioselectivity172.2.3Influenceoftemperature212.2.4InfluenceofCOandH2partialpressures222.3Mechanismofthehydroformylationofvinylandvinylidenicalkenes222.3
8、.1Activationofthecatalystprecursor242.3.2Behavioroftheisomericalkyl-metalintermediatesviadeuterioformylation242.3.3InsituIRinvestigationoftheformationandreactivityofacylrhod
