Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA.
J Am Chem Soc. 2011 Jun 15;133(23):9119-23. doi: 10.1021/ja202954b. Epub 2011 May 18.
Regiocontrol of allylic alkylation reactions involving hard nucleophiles remains a significant challenge and continues to be an active area of research. The lack of general methods in which α-alkylation is favored underscores the need for the development of new processes for achieving this type of selectivity. We report that Cu(I) catalyzes the allylic substitution of phosphorothioate esters with excellent α-regioselectivity, regardless of the nature of the Grignard reagent that is used. To the best of our knowledge, the Cu-catalyzed allylic alkylation of phosphorothioate esters has never been described. We have also developed a simple protocol for inducing high α selectivity starting from secondary allylic halides. This is accomplished by using sodium phosphorothioates as an additive.
涉及硬亲核试剂的烯丙基烷基化反应的区域控制仍然是一个重大挑战，并且仍然是一个活跃的研究领域。缺乏有利于α-烷基化的一般方法突出表明需要开发新的工艺来实现这种选择性。我们报告说，Cu（I）催化膦酸硫酯与格氏试剂的烯丙基取代反应具有出色的α-区域选择性，无论所使用的格氏试剂的性质如何。据我们所知，从未有人描述过 Cu 催化的膦酸硫酯的烯丙基烷基化反应。我们还开发了一种从仲烯丙基卤化物开始诱导高α选择性的简单方案。这是通过使用亚磷酸硫酯钠作为添加剂来实现的。
