On the importance of leaving group ability in reactions of ammonium, oxonium, phosphonium, and sulfonium ylides

被引：91
作者：
Aggarwal, VK [1 ]
Harvey, JN [1 ]
Robiette, R [1 ]
机构：
[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2005年 / 44卷 / 34期
关键词：
density functional calculations; leaving group ability; onium compounds; sigmatropic rearrangement; ylides;
D O I：
10.1002/anie.200501526
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
(Chemical Equation Presented) What controls reactivity of ylides? Computational data show that reactivity in the reactions shown in the scheme is mainly determined by the leaving group ability of the onium group, and this decreases for both intrinsic and thermochemical reasons in the order O > S > N > P. The results are consistent with experimental observations and account for the dearth of examples of phosphorus ylides in these reactions. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.
引用
收藏
页码：5468 / 5471
页数：4
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