at Google ScholarTitle data
Jana, Sripati ; Pei, Chao ; Empel, Claire ; Koenigs, Rene M.:
Photochemical Carbene Transfer Reactions of Aryl/Aryl Diazoalkanes : Experiment and Theory.
In: Angewandte Chemie International Edition.
Vol. 60
(2021)
.
- pp. 13271-13279.
ISSN 1521-3773
DOI: https://doi.org/10.1002/anie.202100299
Abstract in another language
Controlling the reactivity of carbene intermediates is a key parameter in the development of selective carbene transfer reactions and is usually achieved by metal complexes via singlet metal-carbene intermediates. In this combined experimental and computational studies, we show that the reactivity of free diaryl carbenes can be controlled by the electronic properties of the substituents without the need of external additives. The introduction of electron-donating and -withdrawing groups results in a significant perturbation of singlet triplet energy splitting of the diaryl carbene intermediate and of activation energies of consecutive carbene transfer reactions. This strategy now overcomes a long-standing paradigm in the reactivity of diaryl carbenes and allows the realization of highly chemoselective carbene transfer reactions with alkynes. We could show that free diaryl carbenes can be readily accessed via photolysis of the corresponding diazo compounds and that these carbenes can undergo highly chemoselective cyclopropenation, cascade, or C−H functionalization reactions. Experimental and theoretical mechanistic analyses confirm the participation of different carbene spin states and rationalize for the observed reactivity.
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: | 01 Apr 2025 10:57 |
| Last Modified: | 07 Oct 2025 11:01 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/93105 |