Cobalt-Catalyzed Hydrofunctionalizations of Alkenes with sp3-Hybridized Electrophiles

Saturated carbon centers connected with sp3 hybridized atoms are ubiquitous subunits in organic molecules which play an important role in pharmaceuticals, agrochemicals, material sciences. Over the past decades, transition-metal-catalyzed cross-coupling reactions (e.g., Suzuki-Miyaura, Kumada, Negishi, Stille coupling, and Buchwald-Hartwig amination reaction) enabled sp3-sp3 coupling using sp3 nucleophiles and sp3 electrophiles have been evolved into one of the most tools to access such units. However, the preformation and utilization of stoichiometric organometallic reagents, competitive β-H elimination of alkyl metallic intermediates, impose significant challenges and limitations for their further applications. Recent advances in metal-catalyzed hydrofunctionalization of alkenes present a promising alternative by utilizing alkenes as latent alkyl nucleophiles in the presence of a silane, circumventing the use of stoichiometric amount of sp3 hybridized metallic reagents. Over the past years, cobalt catalyzed hydrofunctionalization of alkenes with sp3 hybridized electrophiles has emerged as a compelling approach for sp3-sp3 coupling to forge carbon-carbon and carbon-heteroatom bonds, demonstrating broad functional group compatibility and enhanced regio- and enantioselectivity. This review highlights the advances in cobalt-catalyzed hydrofunctionalizations of alkenes with sp3hybridized electrophiles to form sp3-sp3 bonds, alongside the future research on addressing the existing obstacles in this field.