Flavin Nitroalkane Oxidase Mimics Compatibility with NOx/TEMPO Catalysis: Aerobic Oxidization of Alcohols, Diols, and Ethers
| Autor: | Thanh Thuy Vuong, Frank W. Foss, Shan Hazoor, P. Thapa, Bikash Chouhan |
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| Rok vydání: | 2020 |
| Předmět: |
inorganic chemicals
biology 010405 organic chemistry Organic Chemistry Formaldehyde Flavoprotein Sulfoxide Flavin group 010402 general chemistry 01 natural sciences 0104 chemical sciences Catalysis chemistry.chemical_compound chemistry Nitroalkane oxidase biology.protein Organic chemistry Selectivity NOx |
| Zdroj: | The Journal of Organic Chemistry. 85:9096-9105 |
| ISSN: | 1520-6904 0022-3263 |
| DOI: | 10.1021/acs.joc.0c01013 |
| Popis: | Biomimetic flavin organocatalysts oxidize nitromethane to formaldehyde and NOx-providing a relatively nontoxic, noncaustic, and inexpensive source for catalytic NO2 for aerobic TEMPO oxidations of alcohols, diols, and ethers. Alcohols were oxidized to aldehydes or ketones, cyclic ethers to esters, and terminal diols to lactones. In situ trapping of NOx and formaldehyde suggest an oxidative Nef process reminiscent of flavoprotein nitroalkane oxidase reactivity, which is achieved by relatively stable 1,10-bridged flavins. The metal-free flavin/NOx/TEMPO catalytic cycles are uniquely compatible, especially compared to other Nef and NOx-generating processes, and reveal selectivity over flavin-catalyzed sulfoxide formation. Aliphatic ethers were oxidized by this method, as demonstrated by the conversion of (-)-ambroxide to (+)-sclareolide. |
| Databáze: | OpenAIRE |
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