Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides Using Michael Acceptors

作者：Xiangyu Wu, Wei Hao, Ke‐Yin Ye, Binyang Jiang, Gisselle Pombar, Zhidong Song, Song Lin · 发表于：Journal of the American Chemical Society · 年份：2018 · DOI：10.1021/jacs.8b08605 · 被引用次数：173 · 研究领域：Radical Photochemical Reactions、Catalytic C–H Functionalization Methods、Vanadium and Halogenation Chemistry

Alkyl chlorides are common functional groups in synthetic organic chemistry. However, the engagement of unactivated alkyl chlorides, especially tertiary alkyl chlorides, in transition-metal-catalyzed C–C bond formation remains challenging. Herein, we describe the development of a Ti III -catalyzed radical addition of 2° and 3° alkyl chlorides to electron-deficient alkenes. Mechanistic data are consistent with inner-sphere activation of the C–Cl bond featuring Ti III -mediated Cl atom abstraction. Evidence suggests that the active Ti III catalyst is generated from the Ti IV precursor in a Lewis-acid-assisted electron transfer process.