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

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.