Asymmetric alkene-alkene reductive cross-coupling reaction via visible-light photoredox/cobalt dual catalysis

The first example of asymmetric alkene-alkene reductive coupling is demonstrated via visible-light-fueled photoredox/cobalt dual catalysis. The desymmetrization reaction provided products (>20 examples) with up to five chiral centers in single-step operation in up to 95% yields with very high relative (>99 : 1 dr) and absolute stereochemistry (up to 98 : 2 er) control. The preliminary mechanistic investigations suggested that the critical mechanistic steps involved light-mediated controlled low-valent cobalt complex generation, oxidative ene-ene cyclization, and protonation.

Automated summary

The first example of asymmetric alkene-alkene reductive coupling is demonstrated using visible-light-fueled photoredox/cobalt dual catalysis. The desymmetrization reaction achieves single-step operation with high yields (up to 95%) and excellent control of both relative (>99 : 1 dr) and absolute stereochemistry (up to 98 : 2 er), generating products with up to five chiral centers. Preliminary mechanistic investigations suggest key steps involving light-mediated controlled low-valent cobalt complex generation, oxidative ene-ene cyclization, and protonation.