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

ABSTRACT: The first catalytic enantioselective carbonyl (?-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 (?-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.

SUBMITTER: Spielmann K

PROVIDER: S-EPMC6739137 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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

Spielmann Kim K Xiang Ming M Schwartz Leyah A LA Krische Michael J MJ

Journal of the American Chemical Society 20190829 36

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 st ...[more]

PMID: 31465211

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