The copper-catalyzed highly selective hydrosilylation of silyl or boryl alkene has been developed. This chemistry could afford a practical method for preparing chiral geminated disilyl and borylsilyl reagents, which are useful organosilanes and versatile synthons for organic synthesis. The experimental data suggested that this reaction could be compatible with a variety of functional groups. Furthermore, the utility of the gem-dimetal compounds, which could be prepared by this chemistry, has been well illustrated by further transformations.

Allyl boron derivatives are valuable building blocks in the synthesis of natural products and bioactive molecules. Herein, a practical strategy of nickel-catalyzed highly selective hydroalkenylation of alkenyl boronic esters was developed. Under the mild reaction conditions, a variety of allyl boronic esters were accessed with excellent chemo- and regioselectivity. The mechanism of this transformation was illustrated by control experiments and kinetic studies.

Due to the significance of corresponding products, enantioselective borylative cyclization reactions have been studied intensively in recent years. Many groups have developed efficient methods to transform unsaturated system into asymmetric cyclic organoboron compounds with the ring‐size range from three‐membered to six‐membered in general. Notably, in some cases, fused rings which contain more than two contiguous chiral centers could be obtained by this kind of strategies. This review summarized and reviewed the recent advances in this field and classified these work according to the species of metal catalysts.

The palladium-catalyzed borylative cyclization via C-H activation has been developed. By this chemistry, the indole-fused dihydro-pyrrole motif, which is a kind of important unit in natural products and bio-active molecules, could be constructed and installed with a boric ester group. Furthermore, the utilities of products have been illustrated by the study of further transformations. Importantly, by using chiral ligand, the enantioselectivity of this borylative cyclization reaction could be controlled. Moreover, the borylative mechanism, which should proceed through a Pd(II)/Pd(IV) catalytic cycle, has been proposed based on the DFT calculations.

Comprehensive Summary “Chain‐walking” reactions could realize to modify a molecule at the position far away from the active site. It has been a hot topic in the research field of organic synthesis. As a number of achievements have been made by researchers, the products of transition metal‐catalyzed chain‐walking reactions could be obtained with good enantioselectivity. This review summarized the researches on the asymmetric chain‐walking reactions catalyzed by transition metal in the past decade. These works are classified according to the species of metal catalysts.