Intercepting the Gold-Catalysed Meyer-Schuster Rearrangement by Controlled Protodemetallation: A Regioselective Hydration of Propargylic Alcohols
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- 作者：Matthew N. Pennell ; Michael P. Kyle ; Samantha M. Gibson ; Louise Male ; Peter G. Turner ; Richard S. Grainger and Tom D. Sheppard
- 关键词：aldol reaction ; alkynes ; boronic acids ; enolates ; gold
- 刊名：Advanced Synthesis & Catalysis
- 出版年：2016
- 出版时间：April 28, 2016
- 年：2016
- 卷：358
- 期：9
- 页码：1519-1525
- 全文大小：703K
- ISSN：1615-4169
文摘
The regioselective gold-catalysed hydration of propargylic alcohols to β-hydroxy ketones can be achieved by diverting the gold-catalysed Meyer–Schuster rearrangement through the addition of a protic additive with a pKa of 7–9 such as p-nitrophenol, boric acid or a boronic acid. This provides an interesting alternative to an aldol reaction when combined with the straightforward addition of an alkyne to an aldehyde or ketone. The gold-catalysed reaction of an electron-deficient, sterically hindered propargylic alcohol with a boronic acid led to the formation of an unusually stable cyclic boron enolate.