at Google ScholarTitle data
Hussain, Yaseen ; Empel, Claire ; Koenigs, Rene M. ; Chauhan, Pankaj:
Carbene Formation or Reduction of the Diazo Functional Group? An Unexpected Solvent‐Dependent Reactivity of Cyclic Diazo Imides.
In: Angewandte Chemie International Edition.
Vol. 62
(2023)
.
- e202309184.
ISSN 1521-3773
DOI: https://doi.org/10.1002/anie.202309184
Abstract in another language
The control of the reactivity of diazo compounds is commonly achieved by the choice of a suitable catalyst, e.g. via stabilization of singlet carbenes or radical intermediates. Herein, we report on the light-promoted reactivity of cyclic diazo imides with thiols, where the choice of solvent results in two fundamentally different reaction pathways. In dichloromethane (DCM), a carbene is formed initially and engages in a cascade C−H functionalization/thiolation reaction to deliver indane-fused pyrrolidines in good to excellent yields. When switching to acetonitrile solvent, the carbene pathway is shut down and an unusual reduction of the diazo compound occurs under otherwise identical reaction conditions, where the aryl thiol acts as reductant. A combined set of experimental and computational studies was carried out to obtain mechanistic understanding and to support that indane formation proceeds via the insertion of a triplet carbene, while the reduction of diazo imides proceeds via an electron transfer process.
Further data
| Item Type: | Article in a journal |
|---|---|
| Refereed: | Yes |
| Institutions of the University: | Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry Faculties Faculties > Faculty of Biology, Chemistry and Earth Sciences Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Organic Chemistry II - Bioorganic Chemistry > Chair Organic Chemistry II - Bioorganic Chemistry - Univ.-Prof. Dr. René M. Koenigs Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Organic Chemistry II - Bioorganic Chemistry |
| Result of work at the UBT: | No |
| DDC Subjects: | 500 Science > 540 Chemistry |
| Date Deposited: | 28 Mar 2025 10:15 |
| Last Modified: | 07 Oct 2025 06:47 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/93039 |