X-ray structures and anionotropic rearrangements of di-tert-butyl-substituted thiiranium and thiirenium ions.: A structure-reactivity relationship

被引:42
作者
Destro, R
Lucchini, V
Modena, G
Pasquato, L
机构
[1] Univ Milan, Dipartimento Chim Fis & Elettrochim, I-20133 Milan, Italy
[2] Univ Milan, Ctr CNR CSRSRC, I-20133 Milan, Italy
[3] Univ Venice, Dipartimento Sci Ambientali, I-30123 Venice, Italy
[4] Univ Padua, Dipartimento Chim Organ, I-35131 Padua, Italy
[5] Univ Padua, Ctr CNR Meccanismi Reazoni Organ, I-35131 Padua, Italy
关键词
D O I
10.1021/jo991731o
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The X-ray structures of c-2,t-3-di-tert-butyl-r-1-methylthiiranium 8 BF4-, t-2,t-3-di-tert-butyl-r-1-methylthiiranium ion 10 BF4-, and 2,3-di-tert-butyl-1-methylthiirenium 11 BF4- have been determined. The Delta G(298)double dagger values for the rearrangements from the cis and the trans tert-butyl groups of 8 SbCl6- to thietanium ion (two intramolecular S(N)2 displacements) and for the rearrangement of 11 SbCl6- to thietium ion tan intramolecular S(N)2-Vin displacement) are linearly correlated with the strengths of the C-S breaking bonds, suggesting that the two mechanisms are, in the absence of steric hindrance, uniquely governed by the nucleofugality of the sulfonium leaving group.
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收藏
页码:3367 / 3370
页数:4
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