University of Bordeaux, Institute of Molecular Sciences, UMR-CNRS 5255, 351 cours de la libération, Talence, 33405 Cedex, France.
Org Lett. 2015 Apr 17;17(8):1958-61. doi: 10.1021/acs.orglett.5b00672. Epub 2015 Mar 31.
New bifunctional reagents for free-radical carbo-oximation of olefins have been developed. In this process, a single reagent can act both as a trap for nucleophilic radicals as well as a source of electrophilic radical via an α-scission of an alkylsulfonyl radical. This strategy involving the addition of a C-centered electrophilic radical and an oxime across the double bond of an electron-rich alkene is initiated with a t-BuO radical following an unusual mechanism, supported by both experiments and density functional theory calculations.
已开发出用于自由基碳氧肟化烯烃的新型双功能试剂。在该过程中，单个试剂可以通过烷基磺酰基自由基的α-断裂同时充当亲核自由基的陷阱和亲电自由基的来源。这种涉及在富电子烯烃的双键上加成 C 中心亲电自由基和肟的策略是由 t-BuO 自由基引发的，遵循一种不寻常的机制，实验和密度泛函理论计算都支持该机制。
