title: Catalyst-Controlled Switch in Chemo- and Diastereoselectivities: Annulations of Morita-Baylis-Hillman Carbonates from Isatins.
abstract: Regulating both the chemo- and diastereoselectivity, divergently, of a reaction is highly attractive but extremely challenging. Presented herein is a catalyst-controlled switch in the chemo- and diastereodivergent annulation reactions of Morita-Baylis-Hillman carbonates, derived from isatins and 2-alkylidene-1H-indene-1,3(2H)-diones, in exclusive α-regioselectivity. α-Isocupreine efficiently catalyzed [2+1] reactions to access cyclopropane derivatives, and the diastereodivergent [3+2] annulations were accomplished by employing either a chiral phosphine or a DMAP-type molecule. All reactions exhibited excellent chemoselectivities, and good to remarkable stereoselectivities were furnished, thus leading to a collection of compounds with skeletal and stereogenic diversity. Moreover, DFT computational calculations elucidated the catalyst-based switch in mechanism.
authors.affiliation: Key Laboratory of Drug Targeting and Drug Delivery System of the Ministry of Education, West China School of Pharmacy, and State Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu, 610041, China.
authors.forename: Gu
authors.initials: G
authors.lastname: Zhan
authors.affiliation: Key Laboratory of Drug Targeting and Drug Delivery System of the Ministry of Education, West China School of Pharmacy, and State Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu, 610041, China.
authors.forename: Ming-Lin
authors.initials: ML
authors.lastname: Shi
authors.affiliation: Key Laboratory of Drug Targeting and Drug Delivery System of the Ministry of Education, West China School of Pharmacy, and State Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu, 610041, China.
authors.forename: Qing
authors.initials: Q
authors.lastname: He
authors.affiliation: Key Laboratory of Drug Targeting and Drug Delivery System of the Ministry of Education, West China School of Pharmacy, and State Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu, 610041, China.
authors.forename: Wei-Jia
authors.initials: WJ
authors.lastname: Lin
authors.affiliation: College of Pharmacy, Third Military Medical University, Chongqing, 400038, China. ouyangq@tmmu.edu.cn.
authors.forename: Qin
authors.initials: Q
authors.lastname: Ouyang
authors.affiliation: Key Laboratory of Drug Targeting and Drug Delivery System of the Ministry of Education, West China School of Pharmacy, and State Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu, 610041, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Du
authors.affiliation: Key Laboratory of Drug Targeting and Drug Delivery System of the Ministry of Education, West China School of Pharmacy, and State Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu, 610041, China. ycchen@scu.edu.cn.|College of Pharmacy, Third Military Medical University, Chongqing, 400038, China. ycchen@scu.edu.cn.
authors.forename: Ying-Chun
authors.initials: YC
authors.lastname: Chen
keywords: annulations; density-functional calculations; diastereoselectivity; heterocycles; organocatalysis