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Asymmetric Synthesis of 2 H ‐Azirines with a Tetrasubstituted Stereocenter by Enantioselective Ring Contraction of Isoxazoles
Author(s) -
Okamoto Kazuhiro,
Nanya Atsushi,
Eguchi Akira,
Ohe Kouichi
Publication year - 2018
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.201710920
Subject(s) - stereocenter , enantioselective synthesis , substituent , chemistry , rhodium , stereochemistry , isomerization , diene , catalysis , ligand (biochemistry) , ring (chemistry) , combinatorial chemistry , organic chemistry , receptor , biochemistry , natural rubber
Highly strained 2 H ‐azirines with a tetrasubstituted stereocenter were synthesized by the enantioselective isomerization of isoxazoles with a chiral diene–rhodium catalyst system. The effect of ligands and the coordination behavior support the proposed catalytic cycle in which the coordination site is fixed in favor of efficient enantiodiscrimination by a bulky substituent of the ligand. In silico studies also support the existence of a rhodium–imido complex as a key intermediate for enantiodiscrimination.