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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.
Bd. 60
(2021)
.
- S. 13271-13279.
ISSN 1521-3773
DOI: https://doi.org/10.1002/anie.202100299
Abstract
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.
Weitere Angaben
| Publikationsform: | Artikel in einer Zeitschrift |
|---|---|
| Begutachteter Beitrag: | Ja |
| Institutionen der Universität: | Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie |
| Titel an der UBT entstanden: | Nein |
| Themengebiete aus DDC: | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Eingestellt am: | 01 Apr 2025 10:57 |
| Letzte Änderung: | 01 Apr 2025 10:57 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/93105 |