Smedley, Christopher J, Zheng, Qinheng, Gao, Bing, Li, Suhua, Molino, Andrew, Duivenvoorden, Hendrika M, Parker, Belinda S, Wilson, David JD, Sharpless, K Barry, Moses, John E (March 2019) Bifluoride Ion Mediated SuFEx Trifluoromethylation of Sulfonyl Fluorides and Iminosulfur Oxydifluorides. Angewandte Chemie International Edition, 131 (14). pp. 4600-4604. ISSN 0044-8249
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 (TMSCF3) 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 |
|---|---|
| Subjects: | chemistry > techniques > click chemistry > Accelerated SuFEx Click Chemistry chemistry chemistry > techniques > click chemistry chemistry > techniques |
| CSHL Authors: | |
| Communities: | CSHL labs > Moses lab |
| SWORD Depositor: | CSHL Elements |
| Depositing User: | CSHL Elements |
| Date: | 26 March 2019 |
| Date Deposited: | 03 Oct 2023 20:52 |
| Last Modified: | 02 Feb 2024 20:51 |
| Related URLs: | |
| URI: | https://repository.cshl.edu/id/eprint/41121 |
Actions (login required)
 |
Administrator's edit/view item |