Catalytic enantioselective allylboration of ketones
Catalytic enantioselective allylboration of ketones
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DOI：
10.1021/ja047200l
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发表时间：
2004-07-28
影响因子：
15
通讯作者：
Shibasaki, M
中科院分区：
文献类型：
--
作者：
Wada, R;Oisaki, K;Shibasaki, M
介绍了简单酮的烯丙基硼化和巴豆基硼化反应的第一个催化不对称反应实例。使用3 mol % CuF−iPr-DuPHOS作为手性催化剂和4.5 mol % La（OiPr）3作为助催化剂获得了高的对映选择性（高达93%ee）。机理研究表明，本反应的亲核试剂是烯丙基铜，La（OiPr）3促进烯丙基硼酸酯生成烯丙基铜，而不影响酮烯丙基化反应的过渡态结构.
The first example of catalytic enantioselective allylboration and crotylboration of simple ketones is described. High enantioselectivity (up to 93% ee) was obtained using 3 mol % CuF−iPr-DuPHOS as a chiral catalyst and 4.5 mol % La(OiPr)3as a cocatalyst. Mechanistic studies strongly suggested that the active nucleophile of the present reaction is an allylcopper, and that La(OiPr)3facilitates the generation of an active allylcopper from the allylboronate, without affecting the transition-state structure of the ketone allylation step.