The Newman-Kwart Rearrangement of O-Aryl Thiocarbamates: Substantial Reduction in Reaction Temperatures through Palladium Catalysis

被引：56

作者：

Harvey, Jeremy N. ^{[1
]}

Jover, Jesus ^{[1
]}

Lloyd-Jones, Guy C. ^{[1
]}

Moseley, Jonathan D. ^{[2
]}

Murray, Paul ^{[2
]}

Renny, Joseph S. ^{[1
]}

机构：

[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England

[2] AstraZeneca, Avlon Works, Bristol, Avon, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2009年 / 48卷 / 41期

基金：

英国工程与自然科学研究理事会;

关键词：

homogeneous catalysis; palladium; reaction mechanism; rearrangement; sulfur compounds; THERMAL REARRANGEMENT; THIOCARBONYL COMPOUNDS; ASYMMETRIC CATALYSIS; MICROWAVE SYNTHESIS; COUPLING REACTIONS; LIGANDS; COMPLEXES; CHLORIDES; DERIVATIVES; THIOPHENOLS;

D O I：

10.1002/anie.200903908

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Much cooler: The development of a catalyst for the Newman-Kwart rearrangement allows an escape from the harsh thermal conditions of the standard uncatalyzed reaction (see scheme). Mechanistic investigations, employing kinetic, isotopic labelling (2H, 18O, 34S) and DFT studies, suggest that the reaction proceeds through a fivecentred Pd-S coordinated oxidative addition, with intermolecular exchange of aryl and thiocarbamate moieties through dimerization of the resting state. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：7612 / 7615

页数：4

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