Park, Sooyoung and Dutta, Amit K. and Allacher, Carina and Abramov, Anton and Dullinger, Philipp and Kuzmanoska, Katerina and Fritsch, Daniela and Hitzfeld, Patrick and Horinek, Dominik and Rehbein, Julia and Nuernberger, Patrick and Gschwind, Ruth M. and Breder, Alexander (2022) Hydrogen-Bond-Modulated Nucleofugality of Se-III Species to Enable Photoredox-Catalytic Semipinacol Manifolds. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 61 (49): e202208611. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
Chemical bond activations mediated by H-bond interactions involving highly electronegative elements such as nitrogen and oxygen are powerful tactics in modern catalysis research. On the contrary, kindred catalytic regimes in which heavier, less electronegative elements such as selenium engage in H-bond interactions to co-activate C-Se sigma-bonds under oxidative conditions are elusive. Traditional strategies to enhance the nucleofugality of selenium residues predicate on the oxidative addition of electrophiles onto Se-II-centers, which entails the elimination of the resulting Se-IV moieties. Catalytic procedures in which Se-IV nucleofuges are substituted rather than eliminated are very rare and, so far, not applicable to carbon-carbon bond formations. In this study, we introduce an unprecedented combination of O-H center dot center dot center dot Se H-bond interactions and single electron oxidation to catalytically generate Se-III nucleofuges that allow for the formation of new C-C sigma-bonds by means of a type I semipinacol process in high yields and excellent selectivity.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CENTER-DOT-OP; SCALAR COUPLINGS; ELECTRON-TRANSFER; RING ENLARGEMENT; BETA; REARRANGEMENT; EXPANSION; RADICALS; KETONES; Hydrogen-Bonds; Nucleofugality; Photoredox-Catalysis; Rearrangements; Selenium(III) |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Physical Chemistry I > Prof. Dr. Patrick Nürnberger |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 21 Nov 2023 15:17 |
| Last Modified: | 21 Nov 2023 15:17 |
| URI: | https://pred.uni-regensburg.de/id/eprint/56762 |
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