Day, Jon and Grotjahn, Sascha and Senaweera, Sameera and Koenig, Burkhard and Weaver, Jimmie D. (2021) Defluorodearomatization: A Photocatalytic Birch-Like Reduction That Enables C-C Bond Formation and Provides Access to Unnatural Cannabinoids. JOURNAL OF ORGANIC CHEMISTRY, 86 (12). pp. 7928-7945. ISSN 0022-3263, 1520-6904
Full text not available from this repository. (Request a copy)Abstract
Within the framework of discovery chemistry, polyfluorination remains a synthetic challenge despite its ability to provide useful characteristics, such as a reduction in the number of hydrogen bond donors and metabolic stability. Coupling a reversal of this methodology with photocatalysis has been demonstrated to allow the rapid synthesis of previously difficult or impossible targets by starting with fluorines everywhere and selectively removing or functionalizing them. Herein, we demonstrate a novel method to synthesize 1,4-cyclohexadienes through a dearomative photocatalytic C-C coupling reaction. This allows for access to materials that are orthogonal to the selectivity of the Birch reaction and are more functional-group-tolerant. The reaction also allows the efficient synthesis of polyfluorinated cannabinoids. While the yields are modest, the access to the new chemical space provided by the reaction is unprecedented by any means. The trifluorinated analog of THC, 1-deoxy-1,2,4-trifluoro-THC, is synthesized, demonstrating the importance of discovery chemistry and the ability to explore otherwise unknown structure-activity relationships.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | NUCLEOPHILIC AROMATIC-SUBSTITUTION; VISIBLE-LIGHT; FREE-ENERGY; COMPLEXES; ELECTRON; FLUORINE; RADICALS; FACILE; 1,4-CYCLOHEXADIENE; FUNCTIONALIZATION |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 01 Sep 2022 04:46 |
| Last Modified: | 01 Sep 2022 04:46 |
| URI: | https://pred.uni-regensburg.de/id/eprint/47101 |
Actions (login required)
 |
View Item |
