Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
J Am Chem Soc. 2021 Dec 8;143(48):20071-20076. doi: 10.1021/jacs.1c10756. Epub 2021 Nov 19.
Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, a strategy previously not considered for catalytic H-P bond activation, is at the base of the mechanistic action of the Mn(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enantioselectivity.
在这里，我们报告手性 Mn(I) 配合物能够活化 H-P 键。这种活化模式为内型和末端α,β-不饱和腈的膦氢化提供了一种通用方法。金属-配体协同作用，这是一种以前未被考虑用于催化 H-P 键活化的策略，是基于 Mn(I)基催化剂的机械作用的基础。我们的计算研究支持膦氢化的逐步机理，并提供了对对映选择性起源的深入了解。
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