使用二硫化物作为光催化剂和氢原子穿梭体对烯烃进行一般的反马氏氢膦酰化反应。
General Anti-Markovnikov Hydrophosphinylation of Olefins Using Disulfide as the Photocatalyst and a Hydrogen Atom Shuttle.
作者信息
Zhang Guoxiang, He Hui, Chen Xiaoxiao, Ni Shao-Fei, Zeng Rong
机构信息
School of Chemistry, Xi'an Jiaotong University, Xi'an 710049, P. R. China.
Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong, Shantou University, Shantou 515063, Guangdong, P. R. China.
出版信息
Org Lett. 2023 Jul 21;25(28):5356-5360. doi: 10.1021/acs.orglett.3c01939. Epub 2023 Jul 7.
The photoinduced radical-based hydrophosphinylation suffered from substrate scope limitation due to the highly electrophilic property of the P(O) radical. Herein, we report an efficient catalytic system for the intermolecular anti-Markovnikov hydrophosphinylation of olefins using disulfide as a photocatalyst and also a hydrogen atom shuttle. This metal-free, base-free, and redox-neutral condition allowed the alkenes with diverse electronic properties to proceed with the anti-Markovnikov P-H addition efficiently. A plausible mechanism involving the HAT process between ArS• and P(O)-H was proposed.
由于磷酰基自由基具有高亲电性，基于光诱导自由基的氢膦酰化反应存在底物范围限制。在此，我们报道了一种高效的催化体系，该体系以二硫化物作为光催化剂和氢原子穿梭体，用于烯烃的分子间反马氏氢膦酰化反应。这种无金属、无碱且氧化还原中性的条件使得具有不同电子性质的烯烃能够有效地进行反马氏P-H加成反应。我们提出了一种涉及ArS•与P(O)-H之间氢原子转移（HAT）过程的合理机理。
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