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Improved Catalysts for the Iridium‐Catalyzed Asymmetric Isomerization of Primary Allylic Alcohols Based on Charton Analysis
Author(s) -
Mantilli Luca,
Gérard David,
Torche Sonya,
Besnard Céline,
Mazet Clément
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201001311
Subject(s) - iridium , isomerization , allylic rearrangement , catalysis , cationic polymerization , steric effects , chemistry , ligand (biochemistry) , combinatorial chemistry , organic chemistry , biochemistry , receptor
An improved generation of chiral cationic iridium catalysts for the asymmetric isomerization of primary allylic alcohols is disclosed. The design of these air‐stable complexes relied on the preliminary mechanistic information available, and on Charton analyses using two preceding generations of iridium catalysts developed for this highly challenging transformation. Sterically unbiased chiral aldehydes that were not accessible previously have been obtained with high levels of enantioselectivity, thus validating the initial hypothesis regarding the selected ligand‐design elements. A rationale for the high enantioselectivities achieved in most cases is also presented.