Donabauer, Karsten and Murugesan, Kathiravan and Rozman, Ursa and Crespi, Stefano and Koenig, Burkhard (2020) Photocatalytic Reductive Radical-Polar Crossover for a Base-Free Corey-Seebach Reaction. CHEMISTRY-A EUROPEAN JOURNAL, 26 (57). pp. 12945-12950. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
A metal-free generation of carbanion nucleophiles is of prime importance in organic synthesis. Herein we report a photocatalytic approach to the Corey-Seebach reaction. The presented method operates under mild redox-neutral and base-free conditions giving the desired product with high functional group tolerance. The reaction is enabled by the combination of photo- and hydrogen atom transfer (HAT) catalysis. This catalytic merger allows a C-H to carbanion activation by the abstraction of a hydrogen atom followed by radical reduction. The generated nucleophilic intermediate is then capable of adding to carbonyl electrophiles. The obtained dithiane can be easily converted to the valuable alpha-hydroxy carbonyl in a subsequent step. The proposed reaction mechanism is supported by emission quenching, radical-radical homocoupling and deuterium labeling studies as well as by calculated redox-potentials and bond strengths.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | HYDROGEN-ATOM TRANSFER; ANION RELAY CHEMISTRY; C(SP(3))-H FUNCTIONALIZATION; CARBONYL-COMPOUNDS; COUPLING REACTION; ALDEHYDES; 1,3-DITHIANES; HYDROCARBONS; CYCLIZATION; ACIDITIES; carbanion; Corey-Seebach; HAT-catalysis; photocatalysis; radical-polar crossover |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 11 Mar 2021 12:03 |
| Last Modified: | 11 Mar 2021 12:03 |
| URI: | https://pred.uni-regensburg.de/id/eprint/43784 |
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