中科院上海有机化学研究所李超忠团队报道了钴催化的未活化烯烃与酰基膦酸盐的马氏选择性自由基氢化反应。相关研究成果发表在2021年3月30日出版的《美国化学会杂志》。

具有5，5-二甲基-1，3，2-二氧磷酰基骨架的酰基膦酸盐是一种高效的分子间自由基酰化试剂，能够在温和的室温条件下催化未活化烯烃的Markovnikov氢酰化反应。该方案具有广泛的底物范围和广泛的官能团相容性，以令人满意的产率提供支链酮。该文提出了Co-H介导的氢原子转移和酰基膦酸盐捕获烷基自由基的机理。

具有5,5-二甲基-1,3,2-二氧磷酰基骨架的酰基膦酸盐是一种高效的分子间自由基酰化试剂，可在温和的室温条件下钴催化的未活化烯烃的马氏酰化反应。该方案显示了广泛的底物范围和广泛的官能团相容性，提供了满意的收率的分支酮。提出了Co-H介导的氢原子转移和酰基膦酸盐捕获烷基自由基的机理。

附：英文原文

Title: Cobalt-Catalyzed Markovnikov-Selective Radical Hydroacylation of Unactivated Alkenes with Acylphosphonates

Author: Benxiang Zhang, Jiayan He, Yi Li, Tao Song, Yewen Fang, Chaozhong Li

Issue&Volume: March 30, 2021

Abstract: Acylphosphonates having the 5,5-dimethyl-1,3,2-dioxophosphinanyl skeleton are developed as efficient intermolecular radical acylation reagents, which enable the cobalt-catalyzed Markovnikov hydroacylation of unactivated alkenes at room temperature under mild conditions. The protocol exhibits broad substrate scope and wide functional group compatibility, providing branched ketones in satisfactory yields. A mechanism involving the Co–H mediated hydrogen atom transfer and subsequent trapping of alkyl radicals by acylphosphonates is proposed.

DOI: 10.1021/jacs.1c02629

Source: https://pubs.acs.org/doi/10.1021/jacs.1c02629