Zhang Benxiang, He Jiayan, Li Yi, Song Tao, Fang Yewen, Li Chaozhong
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
School of Materials and Chemical Engineering, Ningbo University of Technology, No. 201 Fenghua Road, Ningbo 315211, China.
J Am Chem Soc. 2021 Apr 7;143(13):4955-4961. doi: 10.1021/jacs.1c02629. Epub 2021 Mar 30.
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.
具有5,5-二甲基-1,3,2-二氧磷杂环己烷基骨架的酰基膦酸酯被开发为高效的分子间自由基酰化试剂，能够在温和条件下于室温实现钴催化的未活化烯烃的马氏氢酰化反应。该方法具有广泛的底物范围和良好的官能团兼容性，能以令人满意的产率提供支链酮。提出了一种涉及钴氢介导的氢原子转移以及随后酰基膦酸酯捕获烷基自由基的机理。
