The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction of complex motifs. Despite remarkable progress, novel and efficient methods for achieving such transformations under milder conditions with chemo-, regio-, and stereoselectivity still remain a significant challenge; thus, their development is highly desirable. Recently, the merging of nickel catalysis with radical chemistry offers a new and benign platform for the catalytic dicarbofunctionalization of unsaturated π bonds with unprecedented reactivity and selectivity. In this review, we summarize the recent advances in this area by underpinning the catalytic domino transformations involving radical capture by nickel to provide a clear overview of reaction designs and mechanistic scenarios.
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