Borohydride intermediates pave the way for magnesium-catalysed enantioselective ketone reduction.
Borohydride intermediates pave the way for magnesium-catalysed enantioselective ketone reduction.
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DOI：
10.1039/c9cc09111d
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发表时间：
2020-01
影响因子：
4.9
通讯作者：
V. Vasilenko;Clemens K. Blasius;H. Wadepohl;L. Gade
中科院分区：
文献类型：
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作者：
V. Vasilenko;Clemens K. Blasius;H. Wadepohl;L. Gade
报道了一种用于C[双键，长度为m-dash]O键硼氢化反应的高不对称选择性镁预催化剂。通过分离催化中间体和理论上的DFT计算，研究了这一前所未有的选择性转化的机理基础。硼氢化镁物质的容易形成在克服选择性决定插入步骤中的竞争途径中是至关重要的。
A magnesium precatalyst for the highly enantioselective hydro-boration of C[double bond, length as m-dash]O bonds is reported. The mechanistic basis of the unprecedented selectivity of this transformation has been investi-gated experimentally by isolation of catalytic intermediates and theoretically by DFT calculations. The facile formation of a magnesium borohydride species is critical in overcoming competing pathways in the selectivity-determining insertion step.