State Key Laboratory of Medical Chemical Biology, College of Pharmacy, Nankai University, 38 Tongyan Road, Jinnan District, Tianjin, 300350, P. R. China.
Angew Chem Int Ed Engl. 2023 Jun 19;62(25):e202301628. doi: 10.1002/anie.202301628. Epub 2023 May 4.
Transition-metal-catalyzed enantioselective P-C cross-coupling of secondary phosphine oxides (SPOs) is an attractive method for synthesizing P-stereogenic phosphorus compounds, but the development of such a dynamic kinetic asymmetric process remains a considerable challenge. Here we report an unprecedented highly enantioselective dynamic kinetic intermolecular P-C coupling of SPOs and aryl iodides catalyzed by copper complexes ligated by a finely modified chiral 1,2-diamine ligand. The reaction tolerates a wide range of SPOs and aryl iodides, affording P-stereogenic tertiary phosphine oxides (TPOs) in high yields and with good enantioselectivity (average 89.2 % ee). The resulting enantioenriched TPOs were transformed into structurally diverse P-chiral scaffolds, which are highly valuable as ligands and catalysts in asymmetric synthesis.
过渡金属催化的手性膦氧化物（SPO）的对映选择性 P-C 交叉偶联是合成 P-手性磷化合物的一种很有吸引力的方法，但开发这种动态动力学不对称过程仍然是一个相当大的挑战。在这里，我们报道了一种前所未有的、高对映选择性的动态动力学分子间 SPO 和芳基碘化物的 P-C 偶联，该反应由精细修饰的手性 1,2-二胺配体配位的铜配合物催化。该反应能容忍广泛的 SPO 和芳基碘化物，以高收率和良好的对映选择性（平均 89.2%ee）得到 P-手性叔膦氧化物（TPO）。所得的对映体富集的 TPO 可以转化为结构多样的 P-手性支架，这些支架作为配体和催化剂在不对称合成中具有很高的价值。
