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Langletz, Tim ; Empel, Claire ; Jana, Sripati ; Koenigs, Rene M.:
Stereoconvergent, photocatalytic cyclopropanation reactions of β-substituted styrenes with ethyl diazoacetate.
In: Tetrahedron Chem.
Bd. 3
(2022)
.
- 100024.
ISSN 2666-951X
DOI: https://doi.org/10.1016/j.tchem.2022.100024
Abstract
Cyclopropanes constitute a pivotal molecular scaffold in medicinal and agrochemical research and find broad applications in marketed drugs and other bioactive compounds. Their synthesis commonly relies on metal-catalyzed carbene transfer reactions that necessitate the utilization of stereochemically defined olefin starting materials, which in turn requires a high stereochemical fidelity in the olefin synthesis step. Herein, we report on a photocatalytic strategy that allows the use of a mixture of the E- and Z-isomers of such olefins and gives access to a single isomer of the cyclopropane product in a stereoconvergent reaction. Experimental and theoretical data suggest the intermediacy of a triplet carbene intermediate that readily reacts with either isomer of the olefin. The intersystem crossing from triplet to singlet state proceeds in a diastereoselective fashion and can rationalize this stereoconvergent reaction. The application of this process was then examined with a diverse set of stereochemical mixtures of double- or triple-substituted olefins that readily undergo cyclopropanation disregarding of the stereochemical fidelity of the used olefin.
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: | 31 Mär 2025 13:39 |
| Letzte Änderung: | 31 Mär 2025 13:39 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/93086 |