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Chiral Primary Amine Catalysis for Asymmetric Mannich Reactions of Aldehydes with Ketimines: Stereoselectivity and Reactivity
Author(s) -
Dai Jun,
Xiong Dan,
Yuan Tengrui,
Liu Juan,
Chen Tao,
Shao Zhihui
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201706304
Subject(s) - stereocenter , chemistry , stereoselectivity , reactivity (psychology) , amine gas treating , catalysis , organic chemistry , mannich reaction , selectivity , organocatalysis , enantioselective synthesis , trifluoromethyl , primary (astronomy) , context (archaeology) , combinatorial chemistry , medicine , paleontology , alternative medicine , physics , pathology , astronomy , biology , alkyl
The application potential of primary amine catalysts in the context of Mannich reactions of aldehydes with ketimines is exemplified by isatin‐derived ketimines and cyclic trifluoromethyl ketimines. Primary amine catalysts exhibit either unusual stereoselectivity or reactivity, which is not observable with secondary amine catalysts. Moreover, reversal of diastereofacial selectivity between primary and secondary amine catalysts is disclosed. These new reactions provide useful methods for the syntheses of chiral 3‐substituted 3‐amino‐2‐oxindoles and dihydroquinazolinones bearing a trifluoromethylated quaternary stereocenter. The synthetic utility of the reactions is demonstrated through the formal synthesis of AG‐041R and DPC 083 and the total synthesis of (−)‐psychotriasine.