Anti-Diastereo- and enantioselective carbonyl crotylation from the alcohol or aldehyde oxidation level employing a cyclometallated iridium catalyst: alpha-methyl allyl acetate as a surrogate to preformed crotylmetal reagents.

ABSTRACT: Under the conditions of transfer hydrogenation employing an ortho-cyclometallated iridium catalyst generated in situ from [Ir(cod)Cl](2), 4-cyano-3-nitrobenzoic acid and the chiral phosphine ligand (S)-SEGPHOS, alpha-methyl allyl acetate couples to alcohols 1a-1j with complete levels of branched regioselectivity to furnish products of carbonyl crotylation 3a-3j, which are formed with good levels of anti-diastereoselectivity and exceptional levels of enantioselectivity. An identical set of optically enriched carbonyl crotylation products 3a-3j is accessible from the corresponding aldehydes 2a-2j under the same conditions, but employing isopropanol as the terminal reductant. Experiments aimed at probing the origins of stereoselection establish a matched mode of ionization for the (R)-acetate

SUBMITTER: Kim IS 

PROVIDER: S-EPMC3165013 | biostudies-literature | 2009 Feb

REPOSITORIES: biostudies-literature