State Key Laboratory of Analytical Chemistry for Life Science, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering , Nanjing University , Nanjing 210023 , China.
Org Lett. 2018 Sep 7;20(17):5523-5527. doi: 10.1021/acs.orglett.8b02540. Epub 2018 Aug 23.
A unified strategy for intermolecular remote C(sp)-H and C-C vinylation of O-acyl oximes with vinyl boronic acids has been achieved. This strategy is enabled by photoreductive generation of iminyl radicals from O-acyl oximes under irradiation by visible light. The translocated carbon-centered radicals, which are generated from the iminyl radicals through 1,5-hydrogen atom transfer or C-C cleavage, can be vinylated with vinyl boronic acids. This strategy opens up a new approach to remote functionalization via C(sp)-H and C-C cleavage and provides an efficient and versatile solution to the synthesis of γ-vinylation of ketones and nitriles.
一种与硼基乙烯基试剂进行分子间远程 C(sp)-H 和 C-C 乙烯基化的统一策略已经被实现。该策略是通过可见光照射下 O-酰基肟的光还原生成亚胺基自由基来实现的。亚胺基自由基通过 1,5-氢原子转移或 C-C 裂解生成迁移的碳中心自由基，这些自由基可以与硼基乙烯基试剂进行乙烯基化。该策略通过 C(sp)-H 和 C-C 裂解开辟了远程官能化的新途径，并为酮和腈的γ-乙烯基化提供了高效、通用的合成方法。
