Palladium/Xiao-Phos-Catalyzed Kinetic Resolution of sec-Phosphine Oxides by P-Benzylation
Palladium/Xiao-Phos-Catalyzed Kinetic Resolution of sec-Phosphine Oxides by P-Benzylation
复制标题
钯/小磷催化对位苄基化动力学拆分仲氧化膦
DOI：
10.1002/anie.202111957
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发表时间：
2021-11-16
影响因子：
16.6
通讯作者：
Zhang, Junliang
中科院分区：
文献类型：
--
作者：
Dai, Qiang;Liu, Lu;Zhang, Junliang
对立体基叔膦和仲膦在不对称催化、材料和药物化学等领域有着广泛的应用，但其实际合成仍然是一个重大的挑战。本文设计了一种由钯/小磷催化的对映选择性p -苄基化反应成功的动力学分解rac-仲磷氧化物。叔膦氧化物和仲膦氧化物的收率和对映纯度都很高（选择性因子高达226.1）。通过简单地制备几种有价值的p手性化合物、双齿配体前体以及过渡金属配合物，进一步证明了其吸引人的合成用途。
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.