Smedley, C. J., Zheng, Q., Gao, B., Li, S., Molino, A., Duivenvoorden, H. M., Parker, B. S., Wilson, D. J. D., Sharpless, K. B., Moses, J. E. (March 2019) Bifluoride Ion Mediated SuFEx Trifluoromethylation of Sulfonyl Fluorides and Iminosulfur Oxydifluorides. Angew Chem Int Ed Engl, 58 (14). pp. 4552-4556. ISSN 1433-7851
Abstract
SuFEx is a new-generation click chemistry transformation that exploits the unique properties of S-F bonds and their ability to undergo near-perfect reactions with nucleophiles. We report here the first SuFEx-based procedure for the efficient synthesis of pharmaceutically important triflones and bis(trifluoromethyl)sulfur oxyimines from sulfonyl fluorides and iminosulfur oxydifluorides, respectively. The new process involves rapid S-F exchange with trifluoromethyltrimethylsilane (TMSCF(3) ) upon activation by potassium bifluoride in anhydrous DMSO. The reaction tolerates a wide selection of substrates and proceeds under mild conditions without need for chromatographic purification. A tentative mechanism is proposed involving nucleophilic displacement of S-F by the trifluoromethyl anion via a five-coordinate intermediate. The utility of late-stage SuFEx trifluoromethylation is demonstrated through the synthesis and selective anticancer properties of a bis(trifluoromethyl)sulfur oxyimine.
| Item Type: | Paper |
|---|---|
| Additional Information: | Angewandte Chemie (International ed. in English) |
| Uncontrolled Keywords: | *SuFEx chemistry *bis(trifluoromethyl)sulfur oxyimines *click chemistry *fluorine *trifluoromethylation |
| Subjects: | chemistry chemistry > techniques > click chemistry chemistry > techniques |
| CSHL Authors: | |
| Communities: | CSHL labs > Moses lab |
| Depositing User: | Matthew Dunn |
| Date: | 26 March 2019 |
| Date Deposited: | 08 Jan 2021 17:14 |
| Last Modified: | 02 Feb 2024 20:52 |
| Related URLs: | |
| URI: | https://repository.cshl.edu/id/eprint/39584 |
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