SYNTHESIS AND REACTIVITY OF STABLE SILYL-SUBSTITUTED NITRILIMINES

被引:26
作者
CASTAN, F
BACEIREDO, A
BIGG, D
BERTRAND, G
机构
[1] CNRS,CHIM COORDINAT LAB,205 ROUTE NARBONNE,F-31077 TOULOUSE,FRANCE
[2] CTR RECH PIERRE FABRE MED,F-81106 CASTRES,FRANCE
关键词
D O I
10.1021/jo00005a026
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The reaction of chlorophosphanes and chlorosilanes with the lithium salts of the (bis(diisopropylamino)-thiophosphoranyl)-, bis(diisopropylamino)phosphanyl)-, (trimethylsilyl)-, and (triisopropylsilyl)diazomethane (1, 4, 5, 6) has been studied. Four isolable nitrilimines XCNNY (X = (iPr2N)2P(S), Y = SiiPr3, 10a; X = (iPr2N)2P, Y = SiPh3, 14a; X = (iPr2N)2P, Y = SiiPr3, 15a; X = Y = SiiPr3, 18a) and three observable nitrilimines (X = (iPr2N)2P(S), Y = SiMe3, 8a; X = (iPr2N)2P(S), Y = SiPh3, 9a; X = (iPr2N)2P, Y = SiMe3, 13a) have been obtained. The factors influencing the stability of nitrilimines are analyzed. Several examples of thermal nitrilimine-diazo rearrangements and photochemical nitrilimine-carbodiimide rearrangements are described. The regioselectivity of the reaction of the observable nitrilimines with methyl acrylate and methyl propiolate is compared to that reported for transient nitrilimines. An example of 1,3-addition of butyllithium to a nitrilimine is given.
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页码:1801 / 1807
页数:7
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