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Catalyst‐Controlled Switch in Chemo‐ and Diastereoselectivities: Annulations of Morita–Baylis–Hillman Carbonates from Isatins
Author(s) -
Zhan Gu,
Shi MingLin,
He Qing,
Lin WeiJia,
Ouyang Qin,
Du Wei,
Chen YingChun
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201510825
Subject(s) - stereocenter , regioselectivity , annulation , chemistry , catalysis , combinatorial chemistry , chemoselectivity , indene , baylis–hillman reaction , stereochemistry , organic chemistry , enantioselective synthesis
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‐1 H ‐indene‐1,3(2 H )‐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.