Chapter 15-Mechanism and Structures in Alcohol Addition Reactions of Disilenes and Silenes (p 827-855)

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1、TheChemistryofOrganicSiliconCompounds.Volume2EditedbyZviRappoportandYitzhakApeloigCopyright¶1998JohnWiley&Sons,Ltd.ISBN:0-471-96757-2CHAPTER15MechanismandstructuresinalcoholadditionreactionsofdisilenesandsilenesHIDEKISAKURAIDepartmentofIndustrialChemistry,FacultyofScienceandTechnology,ScienceUnive

2、rsityofTokyo,Noda,Chiba278,JapanI.INTRODUCTION.....................................827II.DISILENES.........................................828A.EZIsomerizationofDisilenes..........................828B.GenerationofPhenyl-substitutedDisilenes.SpectraandKineticsofAdditionofAlcohols...................

3、..............829C.GenerationofAlkoxy-andAmino-substitutedDisilenes..........831D.RegiochemistryofAdditionofAlcoholstoDisilenes............835E.DiastereochemistryofAdditionofAlcoholstoDisilenes.........839F.CompetitionBetweenNucleophilicandElectrophilicMechanisms...842III.SILENES..................

4、.........................844A.GenerationofSilenes................................844B.NucleophilicAdditiontoSilenes.........................844C.DiastereochemistryofAdditionofAlcoholtoSilene............845IV.CONCLUDINGREMARKS..............................853V.ACKNOWLEDGMENTS.......................

5、.........853VI.REFERENCES.......................................853I.INTRODUCTIONOrganosiliconchemistryhasexpandeditsscopeconsiderablyinthelasttwodecades.Oneofthemostremarkableachievementsistheprogresswhichwasmadeintheelucida-tionofthemechanismsinsiliconchemistry,whichnowbecomecomparabletothoseinc

6、arbonchemistry.Thebehaviorofreactiveintermediatessuchassilylenes1,silylradicals2andsilylanions3,4arewellexplored,althoughthechemistryofsilylcationsisstillcontroversial5.Doubly-bondedsiliconspeciesarenowwellunderstood612buttriply-bondedsiliconisstillelusive.827828HidekiSakuraiThemechanismofsubstitu

7、tionreactionsatsaturatedsiliconcentersiswellstudied,regardingbothkineticsandstereochemistry13,14.Incontrast,additionreactionstounsat-uratedsiliconcenters,suchastodisilenesandsilenes,arerelativelyunexplored.Therea