Cobalt-Catalyzed Hydrofunctionalizations of Alkenes with sp3-Hybridized Electrophiles

Abstract Saturated carbon centers connected with sp3 hybridized atoms are ubiquitous subunits in organic molecules, playing important roles in pharmaceuticals, agrochemicals, and materials science. Over the past decades, transition-metal-catalyzed cross-coupling reactions (e.g., Suzuki–Miyaura, Kumada, Negishi, Stille, and Buchwald–Hartwig amination) have enabled sp3–sp3 coupling using sp3 nucleophiles and sp3 electrophiles, and have evolved into extremely useful tools. However, the preformation and utilization of stoichiometric organometallic reagents, along with competitive β-H elimination of alkyl metallic intermediates, impose significant challenges and limitations for 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 amounts of sp3-hybridized metallic reagents. Over the 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 account highlights the advances in cobalt-catalyzed hydrofunctionalizations of alkenes with sp3-hybridized electrophiles to form sp3–sp3 bonds, alongside a discussion on future research avenues on addressing the existing obstacles in this field. 1 Introduction 2 Cobalt-Catalyzed Hydroalkylation of Alkenes 3 Cobalt-Catalyzed Hydroamination of Alkenes 4 Cobalt-Catalyzed Hydrothiolation of Alkenes 5 Summary and Outlook