title: Improved catalysts for the iridium-catalyzed asymmetric isomerization of primary allylic alcohols based on Charton analysis.
abstract: 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.
authors.affiliation: Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4, Switzerland.
authors.forename: Luca
authors.initials: L
authors.lastname: Mantilli
authors.forename: David
authors.initials: D
authors.lastname: Gérard
authors.forename: Sonya
authors.initials: S
authors.lastname: Torche
authors.forename: Céline
authors.initials: C
authors.lastname: Besnard
authors.forename: Clément
authors.initials: C
authors.lastname: Mazet