To develop innovative photocycloadditions between excited carbonyl compounds with C-C bonds and address the absence of catalytic asymmetric ver-sions,herein we report a chiral Lewis acid-mediated catalytic enantiosele...To develop innovative photocycloadditions between excited carbonyl compounds with C-C bonds and address the absence of catalytic asymmetric ver-sions,herein we report a chiral Lewis acid-mediated catalytic enantioselective formal photocycloaddition of excited triplet aldehydes with C-C bond of ben-zocyclobutenones under low catalyst loading(as low as 0.5 mol%).A series of control experiments and density functional theory calculations have con-firmed the existence of diradical intermediates.The Lu(III)/N,N′-dioxide complex plays a crucial role in not only enhancing phosphorescence emission inten-sity but also extending the triplet lifetimes of alde-hydes,which makes it possible for addressing the formidable issue of enantioselective control with in-volved highly reactive triplet intermediates.This ap-proach offers a straightforward avenue to highly enantioenriched 3,4-dihydroisocoumarins in high yields,some of which exhibited anticancer activity upon testing.展开更多
基金the National Key Research and Development Program of China(grant no.2022YFA1504301)the National Natural Science Foundation of China(grant no.92256302)for financial support.
文摘To develop innovative photocycloadditions between excited carbonyl compounds with C-C bonds and address the absence of catalytic asymmetric ver-sions,herein we report a chiral Lewis acid-mediated catalytic enantioselective formal photocycloaddition of excited triplet aldehydes with C-C bond of ben-zocyclobutenones under low catalyst loading(as low as 0.5 mol%).A series of control experiments and density functional theory calculations have con-firmed the existence of diradical intermediates.The Lu(III)/N,N′-dioxide complex plays a crucial role in not only enhancing phosphorescence emission inten-sity but also extending the triplet lifetimes of alde-hydes,which makes it possible for addressing the formidable issue of enantioselective control with in-volved highly reactive triplet intermediates.This ap-proach offers a straightforward avenue to highly enantioenriched 3,4-dihydroisocoumarins in high yields,some of which exhibited anticancer activity upon testing.
