Co-catalyzed sp3-sp3 coupling enabled by hydrofunctionalization of alkenes with nucleophiles

<h2>ABSTRACT</h2> Complementary to classical transition-metal-catalyzed cross-coupling reactions, transition-metal-catalyzed hydrofunctionalization of alkenes has emerged as a powerful strategy for direct and rapid construction of <i>sp</i>³-<i>sp</i>³ linkages. Among various metals, cobalt has been widely used as a catalyst in the hydrofunctionalization of alkenes, demonstrating versatile catalytic reactivity for both electrophiles and nucleophiles to forge <i>sp</i>³-<i>sp</i>³ bonds. When employing nucleophiles as coupling partners, the hydrofunctionalization reactions usually requires the addition of oxidants, due to the presence of nucleophilic intermediate generated through cobalt-hydride-mediated hydrogen atom transfer (HAT) with alkenes. Cobalt-catalyzed hydrofunctionalizations of alkenes with nucleophiles represent an interesting and emerging strategy due to the use of both reductant and oxidant. This review summarizes the recent development of Co-catalyzed hydrofunctionalization of alkenes with nucleophiles, focusing on the construction of various C(<i>sp</i>³)-X(<i>sp</i>³) bonds (X = N, O, S, F). Future direction of this strategy to broaden the scope of <i>sp</i>³-<i>sp</i>³ bond formation is also discussed.