均分解
激进的
烷基化
光化学
化学
烷基
立体化学
催化作用
有机化学
作者
Wei Liu,Marissa N. Lavagnino,Colin A. Gould,Jesús Alcázar,David W. C. MacMillan
出处
期刊:Science
[American Association for the Advancement of Science (AAAS)]
日期:2021-12-03
卷期号:374 (6572): 1258-1263
被引量:62
标识
DOI:10.1126/science.abl4322
摘要
Bimolecular homolytic substitution (SH2) is an open-shell mechanism that is implicated across a host of biochemical alkylation pathways. Surprisingly, however, this radical substitution manifold has not been generally deployed as a design element in synthetic C–C bond formation. We found that the SH2 mechanism can be leveraged to enable a biomimetic sp3-sp3 cross-coupling platform that furnishes quaternary sp3-carbon centers, a long-standing challenge in organic molecule construction. This heteroselective radical-radical coupling uses the capacity of iron porphyrin to readily distinguish between the SH2 bond-forming roles of open-shell primary and tertiary carbons, combined with photocatalysis to generate both radical classes simultaneously from widely abundant functional groups. Mechanistic studies confirm the intermediacy of a primary alkyl–Fe(III) species prior to coupling and provide evidence for the SH2 displacement pathway in the critical quaternary sp3-carbon bond formation step.
科研通智能强力驱动
Strongly Powered by AbleSci AI