Wang, Shun and Cheng, Bei-Yi and Srsen, Matea and Koenig, Burkhard (2020) Umpolung Difunctionalization of Carbonyls via Visible-Light Photoredox Catalytic Radical-Carbanion Relay. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 142 (16). pp. 7524-7531. ISSN 0002-7863, 1520-5126
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The combination of photoredox catalysis with the Wolff-Kishner (WK) reaction allows the difunctionalization of carbonyl groups by a radical-carbanion relay sequence (photo-Wolff-Kishner reaction). Photoredox initiated radical addition to N-sulfonylhydrazones yields alpha-functionalized carbanions following the WK-type mechanism. With sulfur-centered radicals, the carbanions are further functionalized by reaction with electrophiles including CO2 and aldehydes, whereas CF3 radical addition furnishes a wide range of gem-difluoroalkenes through beta-fluoride elimination of the generated alpha-CF3 carbanions. More than 80 substrate examples demonstrate the broad applicability of this reaction sequence. A series of investigations including radical inhibition, deuterium labeling, fluorescence quenching, cyclic voltammetry, and control experiments support the proposed radical-carbanion relay mechanism.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ALDEHYDE TOSYLHYDRAZONES; GEM-DIFLUOROALKENES; C-F; BOND FORMATION; AZO ANIONS; TRIFLUOROMETHYLATION; ALKYLATION; ALKENES; DIFLUOROOLEFINATION; FUNCTIONALIZATION; |
| 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: | 26 Mar 2021 09:36 |
| Last Modified: | 26 Mar 2021 09:36 |
| URI: | https://pred.uni-regensburg.de/id/eprint/44715 |
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