Mandigma, Mark John P. and Zurauskas, Jonas and MacGregor, Callum and Edwards, Lee J. and Shahin, Ahmed and d'Heureuse, Ludwig and Yip, Philip and Birch, David J. S. and Gruber, Thomas and Heilmann, Joerg and John, Matthew P. and Barham, Joshua P. (2022) An organophotocatalytic late-stage N-CH3 oxidation of trialkylamines to N-formamides with O-2 in continuous flow. CHEMICAL SCIENCE, 13 (7). pp. 1912-1924. ISSN 2041-6520, 2041-6539
Full text not available from this repository. (Request a copy)Abstract
We report an organophotocatalytic, N-CH3-selective oxidation of trialkylamines in continuous flow. Based on the 9,10-dicyanoanthracene (DCA) core, a new catalyst (DCAS) was designed with solubilizing groups for flow processing. This allowed O-2 to be harnessed as a sustainable oxidant for late-stage photocatalytic N-CH3 oxidations of complex natural products and active pharmaceutical ingredients bearing functional groups not tolerated by previous methods. The organophotocatalytic gas-liquid flow process affords cleaner reactions than in batch mode, in short residence times of 13.5 min and productivities of up to 0.65 g per day. Spectroscopic and computational mechanistic studies showed that catalyst derivatization not only enhanced solubility of the new catalyst compared to poorly-soluble DCA, but profoundly diverted the photocatalytic mechanism from singlet electron transfer (SET) reductive quenching with amines toward energy transfer (EnT) with O-2.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PHOTOINDUCED ELECTRON-TRANSFER; SINGLET OXYGEN; PHOTOREDOX CATALYSIS; TERTIARY-AMINES; RUTHENIUM TETROXIDE; AEROBIC OXIDATION; HIGHLY EFFICIENT; DRUG-METABOLISM; DEMETHYLATION; LIGHT |
| Subjects: | 500 Science > 540 Chemistry & allied sciences 600 Technology > 615 Pharmacy |
| Divisions: | Chemistry and Pharmacy > Institute of Pharmacy > Pharmaceutical Biology (Prof. Heilmann) |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 18 Aug 2022 10:22 |
| Last Modified: | 18 Aug 2022 10:22 |
| URI: | https://pred.uni-regensburg.de/id/eprint/46749 |
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