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Pericyclic Cascade with Chirality Transfer: Reaction Pathway and Origin of Enantioselectivity of the Hetero‐Claisen Approach to Oxindoles
Author(s) -
ÇelebiÖlçüm Nihan,
Lam Yuhong,
Richmond Edward,
Ling Kenneth B.,
Smith Andrew D.,
Houk Kendall N.
Publication year - 2011
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.201105412
Subject(s) - pericyclic reaction , chirality (physics) , sigmatropic reaction , stereoselectivity , cycloaddition , chemistry , stereochemistry , claisen rearrangement , cascade , combinatorial chemistry , organic chemistry , physics , particle physics , catalysis , quantum chromodynamics , chromatography , nambu–jona lasinio model , chiral symmetry breaking
A new pericyclic cascade is proposed for the chiral auxiliary‐controlled synthesis of 3,3‐disubstituted oxindoles from nitrones and ketenes. The remarkable acyclic 1,6‐stereochemical induction, hitherto unexplained, is rationalized by a stereoselective 3+2 cycloaddition step, which installs the stereochemistry, and a chirality transfer step facilitated by a hetero‐[3,3]‐sigmatropic rearrangement (see picture; PG=protecting group).