Catalytic Amino Group Transfer Reactions Mediated by Photoinduced Nitrene Formation from Rhodium‐Hydroxamates
Abstract Herein, we report a photocatalytic platform to access transient nitrenoids by designing photo‐responsive neutral rhodium‐hydroxamate complexes. Combined experimental and computational mechanistic studies, including electron paramagnetic resonance (EPR) and mass spectrometric analysis, suggest that electrophilic Fischer‐type Rh‐acylnitrenoid intermediates could be generated via photoactivation of corresponding Rh‐hydroxamates via N‐O bond homolysis and redox event. Moreover, catalytic acylnitrenoid transfer was explored toward the amidation of various hydrocarbons, amines, and alcohols to furnish new N−C, N−N, and N−O bonds.
Authors
- Mi Hee Lim (ORCID: https://orcid.org/0000-0003-3377-4996)
- Jeonguk Kweon (ORCID: https://orcid.org/0000-0002-6892-001X)
- Hoimin Jung (ORCID: https://orcid.org/0000-0002-3026-6577)
- Jong‐Min Suh (ORCID: https://orcid.org/0000-0003-2593-9527)
- Andrés Arribas (ORCID: https://orcid.org/0000-0002-8644-4360)
- Sukbok Chang (ORCID: https://orcid.org/0000-0001-9069-0946)
- Dongwook Kim (ORCID: https://orcid.org/0000-0001-6713-989X)
Institutions
- Korea Advanced Institute of Science and Technology (KR)
- Universidade de Santiago de Compostela (ES)
- Institute for Basic Science (KR)
- Center for Research in Molecular Medicine and Chronic Diseases (ES)
- Centro Singular de Investigación en Química Biológica y Materiales Moleculares
Publication Details
- Journal
- Angewandte Chemie
- Published
- 2025-02-18
- DOI
- https://doi.org/10.1002/ange.202422461
- Primary Topic
- Synthesis and Catalytic Reactions
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Research Foundation
- Chungnam National University
- Pohang University of Science and Technology
- Ministry of Science, ICT and Future Planning
- National Research Foundation of Korea
- Korea Advanced Institute of Science and Technology
- Institute for Basic Science