American Chemical Society
ja9b08715_si_003.cif (1.13 MB)

Direct Conversion of Primary Alcohols to 1,2-Amino Alcohols: Enantioselective Iridium-Catalyzed Carbonyl Reductive Coupling of Phthalimido-Allene via Hydrogen Auto-Transfer

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posted 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 2a2z, 2a′2c′ engage in hydrogen auto-transfer-mediated carbonyl reductive coupling by way of (α-amino)­allyliridium−aldehyde pairs to form vicinal amino alcohols 3a3z, 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.