Bartolo Nicole D, Woerpel K A
Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
J Org Chem. 2020 Jun 19;85(12):7848-7862. doi: 10.1021/acs.joc.0c00481. Epub 2020 May 28.
A radical clock system was developed to investigate single-electron transfer (SET) in the reactions of organomagnesium reagents with carbonyl compounds. The fluorenylcyclopropyl radical clock was selected because it is the fastest known radical clock. Additions of Grignard reagents to aldehydes or methyl ketones provided no evidence for ring-opened products that would indicate reaction through SET. Additions of some Grignard reagents to aromatic ketones, however, resulted in the formation of ring-opened products, suggesting SET.
开发了一种自由基时钟系统，以研究有机镁试剂与羰基化合物反应中的单电子转移（SET）。选择芴基环丙基自由基时钟是因为它是已知最快的自由基时钟。格氏试剂与醛或甲基酮的加成反应没有提供表明通过单电子转移反应的开环产物的证据。然而，一些格氏试剂与芳香酮的加成反应导致了开环产物的形成，表明发生了单电子转移。
