Hui Zhang, Ying-Jie Wang, Hao-Wen Jiang,* and Peng-Fei Xu*
https://doi.org/10.1021/acs.orglett.5c05168
ABSTRACT: Herein, we report a strategy for the methylalkylation of unactivated alkenes via synergistic photoredox/nickel catalysis. This mild transformation employs di-tert-butyl peroxide (DTBP) as a bifunctional reagent, which serves simultaneously as a hydrogen atom transfer (HAT) reagent and a source of methyl radical, thereby facilitating the coupling of malonate-derived radicals with alkenes. By integrating HAT with radical selectivity control, the method enables the formation of two C(sp 3 ) bonds in a single synthetic operation, offering a streamlined route to valuable three-dimensional scaffolds.