Hydroalkylation of Unactivated Olefins with C(sp3)-H Com-pounds Enabled by NiH-Catalyzed Radical Relay

The hydroalkylation reaction of olefins with alkanes is a highly desirable synthetic transformation for the construction of C(sp3)-C(sp3) bonds. However, such transformation has proven to be challenging for unactivated olefins, particularly when the substrates are lack of directing groups or acidic C(sp3)-H bonds. Herein, we address this challenge by merging NiH-catalyzed radical relay strategy with a HAT (hydrogen atom transfer) process. In this catalytic system, a nucleophilic alkyl radical is generated from a C(sp3)-H compound in the presence of a HAT promotor, which couples with an alkyl metallic intermediate generated from the olefin substrate with a NiH catalyst to form the C(sp3)-C(sp3) bond. Notably, this approach represents the first case of transition-metal hydride-catalyzed hydroalkylation of unactivated olefins by employing C(sp3)-H compounds as the alkyl sources. Starting from easily available materials, the reaction not only demonstrates wide func-tional group compatibility but also provides hydroalkylation products with regiodivergency and excellent enantioselectivity through effective catalyst control under mild conditions.