Pennell Matthew N, Kyle Michael P, Gibson Samantha M, Male Louise, Turner Peter G, Grainger Richard S, Sheppard Tom D
Department of Chemistry, University College London Christopher Ingold Laboratories 20 Gordon Street London WC1H 0AJ U.K.
School of Chemistry University of Birmingham Edgbaston, Birmingham B15 2TT U.K.
Adv Synth Catal. 2016 Apr 28;358(9):1519-1525. doi: 10.1002/adsc.201600101. Epub 2016 Apr 27.
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 p of 7-9 such as -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.
通过添加质子添加剂（如对硝基苯酚、硼酸或硼酸酯，其pKa为7-9）来改变金催化的迈耶-舒斯特重排反应，可实现炔丙醇向β-羟基酮的区域选择性金催化水合反应。当与将炔烃直接加成到醛或酮的反应相结合时，这为羟醛反应提供了一种有趣的替代方法。缺电子、空间位阻较大的炔丙醇与硼酸的金催化反应导致形成了一种异常稳定的环状硼烯醇盐。
