Asymmetric counteranion-directed photoredox catalysis

• 成果类型: Article
• 署名作者: Das, Sayantani; Zhu, Chendan; Demirbas, Derya; Bill, Eckhard; De, Chandra Kanta; List, Benjamin
• 署名单位: Max Planck Society; Max Planck Society
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-12555
• DOI: 10.1126/science.ade8190
• 发表日期: 2023-02-03
• 页码: 494-+
• 关键词: lewis-acid catalysis; 2+2 photocycloaddition reactions; cationic-polymerization; dual-catalysis; organocatalyst; acylation

摘要

Photoredox catalysis enables distinctive and broadly applicable chemical reactions, but controlling their selectivity has proven to be difficult. The pursuit of enantioselectivity is a particularly daunting challenge, arguably because of the high energy of the activated radical (ion) intermediates, and previous approaches have invariably required pairing of the photoredox catalytic cycle with an additional activation mode for asymmetric induction. A potential solution for photoredox reactions proceeding via radical ions would be catalytic pairing with enantiopure counterions. However, although attempts toward this approach have been described, high selectivity has not yet been accomplished. Here we report a potentially general solution to radical cation-based asymmetric photoredox catalysis. We describe organic salts, featuring confined imidodiphosphorimidate counteranions that catalyze highly enantioselective [2+2]-cross cycloadditions of styrenes.