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 <i>N</i>-oxide is shown to be broadly applicable. Catalyst screening and optimization showed that a K<sub>2</sub>OsO<sub>2</sub>(OH)<sub>4</sub>-pinacol complex rapidly and chemoselectively reduces the <i>N</i>-oxide cycloadduct in the presence of hydroxylamine and dimethyl sulfoxide. This selectivity was exploited to drive the equilibria toward complex products.
Authors
- Jeffrey W. Keillor (ORCID: https://orcid.org/0000-0002-8133-6862)
- Monica A. Gill (ORCID: https://orcid.org/0000-0002-1238-0042)
- Huy M. Ly (ORCID: https://orcid.org/0000-0002-3530-3330)
- André M. Beauchemin (ORCID: https://orcid.org/0000-0003-0667-6215)
- Hala Almeneim
Institutions
- University of Ottawa (CA)
Publication Details
- Journal
- Organic Letters
- Published
- 2024-11-07
- DOI
- https://doi.org/10.1021/acs.orglett.4c03688
- Citations
- 3
- Primary Topic
- Asymmetric Hydrogenation and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.48
Funders
- University of Ottawa
- Mitacs
- Natural Sciences and Engineering Research Council of Canada