复旦大学张俊良团队报道了钯/磷催化对苄基化动力学拆分仲膦氧化物的方法。相关研究成果发表在2021年10月21日出版的《德国应用化学》。

对立体定向叔膦和仲膦在不对称催化、材料和药物化学中有着广泛的应用，然而，它们的实际合成仍然面临重大的挑战。

该文中，研究人员设计了一种在钯/膦催化下，通过对映选择性对苄基化过程成功拆分肿膦氧化物的动力学方法。叔氧化膦和仲氧化膦的产率和对映体纯度都很高（选择性因子高达226.1）。一些有价值的P-手性化合物、双齿配体的前体以及过渡金属配合物的简便制备进一步证明了该诱人的合成实用性。

附：英文原文

Title: Palladium/Xiao-Phos-Catalyzed Kinetic Resolution  of sec-Phosphine Oxides by P-Benzylation

Author: Junliang Zhang, Qiang Dai, Lu Liu

Issue&Volume: 2021-10-21

Abstract: P-stereogenic tert- and sec-phosphines have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, however, their practical synthesis still constitutes a significant challenge. Herein, a successful kinetic resolution of rac-secondary phosphine oxides via the enantioselective P-benzylation process catalyzed by the palladium/Xiao-Phos was designed. Both tert- and sec-phosphine oxides were delivered in good yield and excellent enantiopurity (selectivity factor up to 226.1). The appealing synthetic utilities are further demonstrated by the facile preparation of several valuable P-chiral compounds, precursors of bidentate ligands, as well as transition metal complexes.

DOI: 10.1002/anie.202111957

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202111957