Wen Xia, Muneer‐ul‐Shafi Bhat, Perla Bharath Kumar, Yu-Long Li, Qiong Yu, Han‐Tong Zhao, Wei Shu
Alkyl–alkyl bonds comprise the majority of the framework of organic molecules, which are ubiquitous in natural products, pharmaceuticals, agrochemicals, and functional materials. Consequently, developing catalytic methods to construct alkyl–alkyl bonds from readily available, cost-effective, and bench-stable precursors is of great importance across organic synthesis, medicinal chemistry, and materials science. Catalytic hydrodimerization of alkenes is among the most direct, atom- and step-economical approaches for forming alkyl–alkyl bonds, using alkenes as the sole precursors. This review systematically discusses advances in catalytic hydrodimerization of alkenes. Various catalytic modes enable hydrodimerization of alkenes under different conditions to access sp 3 -rich architectures with stereochemical control. Notably, cross-hydrodimerization has recently emerged as a promising strategy for asymmetric alkyl–alkyl bond-forming events. Moreover, remaining challenges are highlighted and future directions are outlined in the field.