The article "Enantioselective C(sp³)–C(sp³) Bond Construction by Ni Catalysis" by Li-Ming Chen and Sarah E. Reisman, published in *Accounts of Chemical Research*, reviews recent advances in nickel-catalyzed cross-coupling reactions for forming C(sp³) centers. Nickel, compared to palladium, offers distinct advantages such as facile single-electron transfer to C(sp³) electrophiles and rapid C–C reductive elimination from Ni³⁺, making it well-suited for reductive cross-coupling (RCC) reactions. The authors highlight the use of readily available and stable electrophiles, along with good functional group tolerance, which makes these reactions appealing for complex molecule synthesis. The research is driven by the need to understand factors contributing to enantioinduction and electrophile activation. The article is organized by the identity of the C(sp³) electrophiles, including benzylic chlorides, N-hydroxysphthalamide (NHP) esters, and α-chloro esters and nitriles. The selection of specific chiral ligands plays a crucial role in achieving high cross-selectivity and enantioselectivity. The use of homogeneous reductants, such as tetrakis(dimethylamino)ethylene (TDAE), and electrochemical methods for reduction are also discussed. The authors have developed methods for enantioselective RCCs using various C(sp³) electrophiles, including benzylic chlorides, NHP esters, and α-chloro esters. They have also explored the use of BF₃K salts under metallaphotoredox conditions. The article provides insights into the mechanisms of these reactions, emphasizing the importance of balanced activation rates of electrophiles. The research has expanded the scope of Ni-catalyzed cross-coupling reactions, offering opportunities for the synthesis of diverse and intricate molecules. The authors anticipate that continuous development will further expand the applications of Ni-catalyzed enantioselective RCCs in complex molecule synthesis.The article "Enantioselective C(sp³)–C(sp³) Bond Construction by Ni Catalysis" by Li-Ming Chen and Sarah E. Reisman, published in *Accounts of Chemical Research*, reviews recent advances in nickel-catalyzed cross-coupling reactions for forming C(sp³) centers. Nickel, compared to palladium, offers distinct advantages such as facile single-electron transfer to C(sp³) electrophiles and rapid C–C reductive elimination from Ni³⁺, making it well-suited for reductive cross-coupling (RCC) reactions. The authors highlight the use of readily available and stable electrophiles, along with good functional group tolerance, which makes these reactions appealing for complex molecule synthesis. The research is driven by the need to understand factors contributing to enantioinduction and electrophile activation. The article is organized by the identity of the C(sp³) electrophiles, including benzylic chlorides, N-hydroxysphthalamide (NHP) esters, and α-chloro esters and nitriles. The selection of specific chiral ligands plays a crucial role in achieving high cross-selectivity and enantioselectivity. The use of homogeneous reductants, such as tetrakis(dimethylamino)ethylene (TDAE), and electrochemical methods for reduction are also discussed. The authors have developed methods for enantioselective RCCs using various C(sp³) electrophiles, including benzylic chlorides, NHP esters, and α-chloro esters. They have also explored the use of BF₃K salts under metallaphotoredox conditions. The article provides insights into the mechanisms of these reactions, emphasizing the importance of balanced activation rates of electrophiles. The research has expanded the scope of Ni-catalyzed cross-coupling reactions, offering opportunities for the synthesis of diverse and intricate molecules. The authors anticipate that continuous development will further expand the applications of Ni-catalyzed enantioselective RCCs in complex molecule synthesis.