Recent Advances in Cr-Catalyzed Asymmetric Nozaki–Hiyama–Kishi Reaction: From Alkyl Electrophiles to Alkyl Nucleophiles

Abstract The Nozaki–Hiyama–Kishi (NHK) reaction is renowned for its excellent chemoselectivity and functional-group compatibility in carbonyl additions, and it has been widely applied in natural product synthesis. However, its development has remained relatively dormant for a long time, largely due to restricted diversity of radical precursors, the narrow structural diversity of products, and the need for stoichiometric metal reductants and dissociating reagents. Recently, the reaction has witnessed significant progress, driven by advances in asymmetric radical chemistry, as well as photochemistry and electrochemistry. In this review, we summarize key developments in chromium-catalyzed, asymmetric NHK reactions over the past decade, covering substrate scope, stereocontrol, and mechanistic insights, and discuss the opportunities and challenges that remain in this field.