Enabling Unfavorable Hydroamination Reactions Using a Chemoselective N–O Bond Reduction

Despite major advances, intramolecular alkene hydroamination reactions often face limitations. Herein, a redox-enabled process featuring oxidation of an amine to a hydroxylamine, a concerted hydroamination step, followed by catalytic reduction of N-oxide is shown to be broadly applicable. Catalyst s...

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Bibliographic Details
Published in:Organic letters 2024-11, Vol.26 (46), p.9885-9890
Main Authors: Ly, Huy M., Almeneim, Hala, Gill, Monica A., Keillor, Jeffrey W., Beauchemin, André M.
Format: Article
Language:English
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Summary:Despite major advances, intramolecular alkene hydroamination reactions often face limitations. Herein, a redox-enabled process featuring oxidation of an amine to a hydroxylamine, a concerted hydroamination step, followed by catalytic reduction of N-oxide is shown to be broadly applicable. Catalyst screening and optimization showed that a K2OsO2(OH)4–pinacol complex rapidly and chemoselectively reduces the N-oxide cycloadduct in the presence of hydroxylamine and dimethyl sulfoxide. This selectivity was exploited to drive the equilibria toward complex products.
ISSN:1523-7060
1523-7052
1523-7052
DOI:10.1021/acs.orglett.4c03688