近日，美国加州大学洛杉矶分校Doyle, Abigail G.团队研究了膦氧化还原催化末端烯烃的马尔可夫尼科夫氢胺化反应。该项研究成果发表在2026年2月23日出版的《自然》杂志上。

能够模拟过渡金属反应活性的主族催化剂可拓展底物耐受范围，并实现当前金属催化无法完成的转化。P^III和P^V磷中间体能够发生类似过渡金属的双电子反应这一发现引发思考：P^IV自由基中间体是否能模拟有机金属化学中的其他基元步骤？

研究组报道了一种膦-光氧化还原催化剂体系，可促进未活化末端烯烃与多类N–H唑类化合物的分子间马氏氢胺化反应，这是后过渡金属催化无法实现的转化。实验和计算机理研究揭示了主族催化中一个新的基元步骤：膦自由基阳离子活化烯烃，从而被唑类化合物亲核胺化——该步骤通常与过渡金属催化相关。鉴于亲电烯烃官能团化在过渡金属催化中的广泛应用价值，这种P^IV机制或为主族元素催化及化学合成开辟新机遇。

附：英文原文

Title: Markovnikov hydroamination of terminal alkenes via phosphine redox catalysis

Author: Fan, Flora, Sedillo, Kassandra F., Maertens, Alexander J., Doyle, Abigail G.

Issue&Volume: 2026-02-23

Abstract: Main-group catalysts that mimic transition metal reactivity can expand substrate tolerance and enable transformations not currently possible with metal catalysis1. The discovery that PIII and PV phosphorus intermediates can undergo transition metal-like two-electron chemistry raises the question whether radical PIV intermediates can mimic other elementary steps in organometallic chemistry2,3. Here we describe a phosphine-photoredox catalyst system that promotes intermolecular Markovnikov hydroamination of unactivated terminal alkenes with numerous classes of N–H azoles, a reaction that is not possible with late transition metal catalysis. Experimental and computational mechanistic studies support a new elementary step for main group catalysis wherein a phosphine radical cation activates the alkene to nucleophilic amination by the azole, a step otherwise associated with transition metals. Given the broad value of nucleophilic alkene functionalization in transition metal catalysis, this PIV mechanism could offer new opportunities for main group element catalysis and chemical synthesis.

DOI: 10.1038/s41586-026-10263-7

Source: https://www.nature.com/articles/s41586-026-10263-7