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Empel, Claire ; Pei, Chao ; He, Feifei ; Jana, Sripati ; Koenigs, Rene M.:
Proton or Carbene Transfer? On the Dark and Light Reaction of Diazoalkanes with Alcohols.
In: Chemistry : a European Journal.
Bd. 28
(2022)
.
- e202104397.
ISSN 1521-3765
DOI: https://doi.org/10.1002/chem.202104397
Abstract
The formal alkylation reaction of OH groups with diazoalkanes under catalyst-free reaction conditions finds broad application in organic synthesis. However, even today, this reaction is mainly limited to the use of diazomethane as reaction partner. In this combined experimental and theoretical study, we aim at a fundamental understanding of the reaction of diazoalkanes with alcohols to make this transformation amenable to a generalized approach towards formal alkylation reactions of alcohols with diazoalkanes. Experimental and theoretical studies suggest a direct proton transfer only in exceptional cases. In a more general setting, such O−H functionalization proceed both under dark and photochemical conditions via a key hydrogen-bonded singlet carbene intermediate that undergoes a protonation–addition mechanism. We conclude with applications of this approach in O−H functionalization reactions of alcohols, including simple fluorinated, halogenated and aliphatic alcohols and showcase functional-group tolerance of this method in the reaction of biologically active and pharmaceutically relevant alcohols.
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 08:48 |
| Letzte Änderung: | 01 Apr 2025 08:48 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/93100 |