Vinylogous reaction serves as an efficient tool to introduce a new functional group at the γ-position (or even more remote position) of the parent functional group. The produced highly functionalized structure motifs (especially chiral ones) are ubiquitous in natural products, biologically active compounds and pharmaceuticals. Moreover, they work as important synthetic intermediates in organic syntheses. Therefore, asymmetric vinylogous reaction has gained extensive attention in recent years. Our group is interested in the development of efficient direct vinylogous reactions by using copper catalysts with a focus on the catalytic asymmetric variants. Herein, the advances in our group in this field are reviewed. Both α,β-unsaturated and β,γ-unsaturated compounds (including esters, aldehydes, ketones, phosphonates, sulfones, and nitriles) are used as the vinylogous pronucleophiles. Aldehydes, ketones, imines, and molecular oxygen are employed as the electrophiles. This account is divided into three sections based on the varied electrophiles: asymmetric vinylogous aldol reaction, asymmetric vinylogous Mannich reaction and vinylogous aerobic oxidative hydroxylation. By using suitable copper catalysts, these reactions generally afforded the vinylogous products in good to excellent yields with good to excellent control of regio-, diastereo-, and enantioselectivities.

Key words: vinylogous reaction, copper catalysis, asymmetric catalysis, aldol reaction, Mannich reaction, oxidative hydroxylation