厦门大学唐果团队报道了脂肪酸的脱羧选择性磷酸化，白磷合成二烷基和三烷基膦氧化物的过渡金属和光催化方法。相关研究成果于2022年9月16日发表于国际一流学术期刊《德国应用化学》。

为白磷（P4）的直接功能化（无氯化）开发实用且温和的策略是一项诱人但艰巨的挑战。

该文中，研究人员报道了在制备结构多样的二烷基膦和三烷基膦方面的突破，这些膦依赖于N-羟基邻苯二甲酰亚胺（NHPI）酯连续生成碳中心自由基，以及在无过渡金属和光催化剂的条件下P4分子的可控烷基化。为了便于分离并防止提纯过程中产品损失，分离出相应的氧化产物二烷基膦氧化物（DAPOs）和三烷基膦氧化合物（TAPOs）。

这种光诱导磷酸化反应具有一锅操作、高产品选择性和耐受范围广泛的烷基NHPI酯，包括复杂天然产物和药物的衍生物。研究同时展示了DAPOs进一步多样化转化，以构建P-F、P-C、P-N和P-O键。

附：英文原文

Title: Decarboxylative Selective Phosphorylation of Aliphatic Acids: A Transition-Metal- and Photocatalyst-Free Avenue to Dialkyl and Trialkyl Phosphine Oxides from White Phosphorus

Author: Fushan Chen, Mengpei Bai, Yumeng Zhang, Weijie Liu, Xinlei Huangfu, Yan Liu, Guo Tang, Yufen Zhao

Issue&Volume: 2022-09-16

Abstract: Developing practical and mild strategies for the direct functionalization of white phosphorus (P  4  ) without chlorination is an appealing but formidable challenge. Toward this end, we report a breakthrough in the preparation of structurally diverse dialkylphosphines and trialkylphosphines that rely on the successive generation of carbon-centered radicals from  N  -hydroxyphthalimide (NHPI) esters and the controllable alkylation of the P  4  molecule under transition-metal- and photocatalyst-free conditions. To facilitate separation and prevent product losses during purification, the corresponding oxidation products dialkylphosphine oxides (DAPOs) and trialkylphosphine oxides (TAPOs) were isolated. This photoinduced phosphorylation reaction features one-pot operation, high product selectivity, and tolerates a broad range of alkyl NHPI esters, including derivatives of complex natural products and pharmaceuticals. Further diversified transformation of DAPOs to construct P–F, P–C, P–N and, P–O bonds was also demonstrated.

DOI: 10.1002/anie.202210334

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202210334