10.1021/jacs.8b08605.s002 Xiangyu Wu Xiangyu Wu Wei Hao Wei Hao Ke-Yin Ye Ke-Yin Ye Binyang Jiang Binyang Jiang Gisselle Pombar Gisselle Pombar Zhidong Song Zhidong Song Song Lin Song Lin Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides Using Michael Acceptors American Chemical Society 2018 Ti IV precursor Cl atom abstraction Ti-Catalyzed Radical Alkylation Tertiary Alkyl Chlorides Lewis-acid-assisted electron transfer process Ti III Michael Acceptors Alkyl chlorides unactivated alkyl chlorides Ti III catalyst bond 2018-10-10 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Ti-Catalyzed_Radical_Alkylation_of_Secondary_and_Tertiary_Alkyl_Chlorides_Using_Michael_Acceptors/7256162 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<sup>III</sup>-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<sup>III</sup>-mediated Cl atom abstraction. Evidence suggests that the active Ti<sup>III</sup> catalyst is generated from the Ti<sup>IV</sup> precursor in a Lewis-acid-assisted electron transfer process.