Benzylic Newman-Kwart rearrangement of O-azidobenzyl thiocarbamates triggered by phosphines: pseudopericyclic [1,3] shifts via uncoupled concerted mechanisms

被引：10
作者：
Alajarin, Mateo [1 ]
Marin-Luna, Marta [1 ]
Ortin, Maria-Mar [1 ]
Sanchez-Andrada, Pilar [1 ]
Vidal, Angel [1 ]
机构：
[1] Univ Murcia, Dept Quim Inorgan, Fac Quim, Murcia 30100, Spain
来源：
TETRAHEDRON | 2009年 / 65卷 / 12期
关键词：
Thiocarboxylates; Thione-thiol rearrangement; Pseudosigmatropic shift; Iminophosphoranes; DENSITY-FUNCTIONAL THEORY; PYRIDINE N-OXIDES; INTRAMOLECULAR ADDITION; AB-INITIO; O; S-DIALKYL DITHIOCARBONATES; S; CONVENIENT SYNTHESIS; THIOL REARRANGEMENT; KETENIMINES; DERIVATIVES;
D O I：
10.1016/j.tet.2009.01.064
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A series of O-(o- and p-azido)benzyl thiocarbamates smoothly rearranged in the course of Staudinger imination reactions with tertiary phosphines, giving rise to the respective S-(o- and p-phosphinimino)benzyl thiocarbamates as a result of an oxygen to Sulfur migration of the functionalized benzyl group. By contrary, their m-azido isomers did not rearrange under similar conditions. Computational investigations using DFT methods revealed the uncoupled concerted mechanisms of these 1,3-benzyl shifts via polar transition states with pseudopericyclic orbital topologies, with the benzyl group migrating in the plane of the thiocarbamate fragment. (c) 2009 Elsevier Ltd. All rights reserved.
引用
收藏
页码：2579 / 2590
页数：12
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