Catalytic Amino Group Transfer Reactions Mediated by Photoinduced Nitrene Formation from Rhodium‐Hydroxamates
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)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-02-18
- DOI
- https://doi.org/10.1002/anie.202422461
- Citations
- 4
- Primary Topic
- Synthesis and Catalytic Reactions
- Type
- article
- Field-Weighted Citation Impact
- 3.74
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