Regioselective Dihalohydration Reactions of Propargylic Alcohols: Gold-Catalyzed and Noncatalyzed Reactions

被引：52

作者：

D'Oyley, Jarryl M. ^{[1
]}

Aliev, Abil E. ^{[1
]}

Sheppard, Tom D. ^{[1
]}

机构：

[1] UCL, Dept Chem, London WC1H 0AJ, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 40期

基金：

英国工程与自然科学研究理事会;

关键词：

gold; halogenation; homogeneous catalysis; ketones; reaction mechanisms; MEYER-SCHUSTER REARRANGEMENT; ORGANOGOLD COMPOUNDS; TERMINAL ALKYNES; EFFICIENT; KETONES; REDUCTION; ALDEHYDES; OLEFINATION; CONVERSION; MECHANISM;

D O I：

10.1002/anie.201405348

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The regioselective conversion of propargylic alcohols into previously unreported alpha, alpha-diiodo-beta-hydroxyketones was achieved by treatment with N-iodosuccinimide in the presence of a gold catalyst. The corresponding alpha, alpha-dichloro-beta-hydroxyketones were obtained by treatment with trichloroisocyanuric acid in the absence of a catalyst. The latter reaction can be extended to other alkynols. These transformations can be used to prepare potentially useful halogenated building blocks. Preliminary mechanistic studies suggest that the reaction involves participation of the acetonitrile solvent in the formation of a 5-halo-1,3-oxazine intermediate.

引用

页码：10747 / 10750

页数：4

共 56 条

[1] Reactions of tertiary propargyl alcohols with sodium halides under oxidative conditions [J].