title: Asymmetric Iridium-Catalyzed C-C Coupling of Chiral Diols via Site-Selective Redox-Triggered Carbonyl Addition.
abstract: Cyclometalated π-allyliridium C,O-benzoate complexes modified by axially chiral chelating phosphine ligands display a pronounced kinetic preference for primary alcohol dehydrogenation, enabling highly site-selective redox-triggered carbonyl additions of chiral primary-secondary 1,3-diols with exceptional levels of catalyst-directed diastereoselectivity. Unlike conventional methods for carbonyl allylation, the present redox-triggered alcohol C-H functionalizations bypass the use of protecting groups, premetalated reagents, and discrete alcohol-to-aldehyde redox reactions.
authors.affiliation: Department of Chemistry, University of Texas at Austin, 1 University Station - A5300, Austin, TX, 78712-1167, USA.
authors.forename: Inji
authors.initials: I
authors.lastname: Shin
authors.affiliation: Department of Chemistry, University of Texas at Austin, 1 University Station - A5300, Austin, TX, 78712-1167, USA. mkrische@mail.utexas.edu.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry; D002384:Catalysis; D007495:Iridium / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D000438:Alcohols; D000447:Aldehydes; D007495:Iridium
keywords: Allylation; Dehydrogenation; Diastereoselectivity; Enantioselectivity; Green chemistry; Iridium; Polyketides; Transfer hydrogenation