Nickel-Catalyzed Negishi-Type Arylation of Trialkylsulfonium Salts
Nickel-Catalyzed Negishi-Type Arylation of Trialkylsulfonium Salts
复制标题
DOI：
10.1055/s-0040-1707817
复制
发表时间：
2020-06
期刊：
影响因子：
2
通讯作者：
H. Yorimitsu;H. Minami;K. Nogi
中科院分区：
文献类型：
--
作者：
H. Yorimitsu;H. Minami;K. Nogi
本文报道了在镍催化下三烷基硫鎓盐与芳基锌试剂的Negishi型芳基化反应。发现使用环己基乙撑作为另外的配体对于促进C-S裂解特别重要。本反应通过与MeOTf的S-甲基化结合来适应二烷基硫化物的一锅芳基化。机理实验表明，C-S裂解将通过单电子转移（SET）进行，以产生最稳定的碳中心自由基，硫醇配体将促进C-S裂解和自由基重组步骤。
Abstract Negishi-type arylation of trialkylsulfonium salts with arylzinc reagents has been accomplished under nickel catalysis. The use of cyclohexanethiol as an additional ligand was found to be particularly important to promote C–S cleavage. The present reaction accommodates one-pot arylation of dialkyl sulfides by combining with S-methylation with MeOTf. Mechanistic experiments suggest that C–S cleavage would proceed via single-electron transfer (SET) to generate the most stable carbon-centered radical and that the thiolate ligand would promote the C–S cleavage and radical recombination step.