Zhang Ya-Qian, Han Xue-Yu, Wu Yue, Qi Peng-Jia, Zhang Qing, Zhang Qing-Wei
Department of Chemistry, University of Science and Technology of China Hefei 230026 China
Chem Sci. 2022 Mar 10;13(14):4095-4102. doi: 10.1039/d2sc00091a. eCollection 2022 Apr 6.
The catalytic asymmetric synthesis of -stereogenic phosphines is an efficient strategy to access structurally diverse chiral phosphines that could serve as organocatalysts and ligands to transition metals and motifs of antiviral drugs. Herein, we describe a Ni catalyzed highly regio and enantioselective hydrophosphinylation reaction of secondary phosphine oxides and enynes. This method afforded a plethora of alkenyl phosphine oxides which could serve as valuable precursors to bidentate ligands. A new type of mechanism was discovered by combined kinetic studies and density functional theory (DFT) calculations, which was opposed to the widely accepted Chalk-Harrod type mechanism. Notably, the alkene moiety which could serve as a directing group by coordinating with the Ni catalyst in the transition state, plays a vital role in determining the reactivity, regio and enantioselectivity.
催化不对称合成α-手性膦是一种有效策略，可用于获得结构多样的手性膦，这些手性膦可作为有机催化剂、过渡金属配体以及抗病毒药物的结构单元。在此，我们描述了一种镍催化的二级膦氧化物与烯炔的高度区域和对映选择性氢膦酰化反应。该方法提供了大量的烯基膦氧化物，它们可作为双齿配体的有价值前体。通过动力学研究和密度泛函理论（DFT）计算相结合，发现了一种新型机理，该机理与广泛接受的查尔克-哈罗德型机理相反。值得注意的是，在过渡态中可通过与镍催化剂配位作为导向基团的烯烃部分，在决定反应性、区域选择性和对映选择性方面起着至关重要的作用。
