Direct Conversion of Primary Alcohols to 1,2-Amino Alcohols: Enantioselective Iridium-Catalyzed Carbonyl Reductive Coupling of Phthalimido-Allene via Hydrogen Auto-Transfer
datasetposted on 2019-08-29, 14:05 authored by Kim Spielmann, Ming Xiang, Leyah A. Schwartz, Michael J. Krische
The first catalytic enantioselective carbonyl (α-amino)allylations are described. Phthalimido-allene 1 and primary alcohols 2a–2z, 2a′–2c′ engage in hydrogen auto-transfer-mediated carbonyl reductive coupling by way of (α-amino)allyliridium−aldehyde pairs to form vicinal amino alcohols 3a–3z, 3a′–3c′ with high levels of regio-, anti-diastereo-, and enantioselectivity. Reaction progress kinetic analysis and isotopic labeling studies corroborate a catalytic cycle involving turnover-limiting alcohol dehydrogenation followed by rapid allene hydrometalation.