Wurzer, Nikolai and Klimczak, Urszula and Babl, Tobias and Fischer, Sebastian and Angnes, Ricardo A. and Kreutzer, Dominik and Pattanaik, Aryaman and Rehbein, Julia and Reiser, Oliver (2021) Heck-Type Coupling of Fused Bicyclic Vinylcyclopropanes: Synthesis of 1,2-Dihydropyridines, 2,3-Dihydro-1H-azepines, 1,4-Cyclohexadienes, and 2H-Pyrans. ACS CATALYSIS, 11 (19). pp. 12019-12028. ISSN 2155-5435
Full text not available from this repository. (Request a copy)Abstract
Herein, we report a versatile approach for the endocyclic ring opening of bicyclic vinylcyclopropanes triggered by Heck arylations. The key step for this transformation is a beta-C-elimination allowing the ring expansion of cyclopropanated pyrroles, piperidines, furans, as well as cyclopentadienes to grant access to the corresponding 1,2-dihydropyridines, 2H-pyrans, 2,3-dihydro-1H-azepines, and 1,4-cyclohexadienes, respectively. Additionally, gem-disubstituted cyclopropanated furans showed unexpected behavior by giving diastereoselectively asymmetrically substituted dienes. Mechanistic studies and theoretical calculations point toward a facile beta-C-elimination with a concomitant shift of Pd along the cyclopropane moiety, which can successfully compete with the usual termination step of a Heck reaction via a syn-beta-hydride elimination.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CARBENE MIGRATORY INSERTION; ARYLBORONIC ACIDS; PALLADIUM(II) CATALYSIS; 3+2 CYCLOADDITION; HETPHOX LIGANDS; BOND FORMATION; BASE-FREE; REARRANGEMENT; EFFICIENT; METAL; donor-acceptor cyclopropanes; Heck coupling; 1,2-dihydropyridines; 2H-pyrans; 2,3-dihydro-1H-azepines; 1,4-cyclohexadienes |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Oliver Reiser |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 07 Jul 2022 08:51 |
| Last Modified: | 07 Jul 2022 08:51 |
| URI: | https://pred.uni-regensburg.de/id/eprint/45899 |
Actions (login required)
 |
View Item |
