MgO-Promoted [4 + 2] Cyclization Using HFA·3H <sub>2</sub> O/SOCl <sub>2</sub> /PPh <sub>3</sub> : Modular Synthesis of <i>gem</i> -Bis(trifluoromethyl)dihydrothiopyrans
The present study reports an unprecedented [4 + 2] annulation for the modular synthesis of gem -bis(trifluoromethyl)-3,6-dihydro-2 H -thiopyrans. The transformation employs readily available HFA·3H 2 O and SOCl 2 as a convenient (CF 3 ) 2 C═S surrogate in the presence of PPh 3, with MgO promoting the subsequent thia -Diels–Alder reaction of 1,3-dienes. The method features a broad substrate scope, excellent practicality for gram-scale synthesis and late-stage functionalization of biologically active molecules, as well as versatile product derivatization. Mechanistic studies identify hexafluoroisopropyl polysulfide species as key intermediates in this process.
Authors
- Zhong‐Xing Jiang (ORCID: https://orcid.org/0000-0003-2601-4366)
- Zhenling Chen
- Pei Meng (ORCID: https://orcid.org/0000-0002-2186-1622)
- Zeng Zr
- Yongcun Shen (ORCID: https://orcid.org/0000-0001-9625-9348)
- Y W Sun (ORCID: https://orcid.org/0000-0002-4420-5708)
- Zhigang Yang (ORCID: https://orcid.org/0000-0002-4857-4850)
- Junyi Rao
- Lu Xiang
Institutions
- Wuhan University of Technology (CN)
- Chinese Academy of Sciences (CN)
- Wuhan University (CN)
- Wuhan Institute of Physics and Mathematics (CN)
- Zhongnan Hospital of Wuhan University (CN)
- Guizhou Institute of Technology (CN)
Publication Details
- Journal
- Organic Letters
- Published
- 2026-07-23
- DOI
- https://doi.org/10.1021/acs.orglett.6c02442
- Primary Topic
- Fluorine in Organic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- Guizhou Institute of Technology
- Zhongnan Hospital of Wuhan University
- Science and Technology Program of Guizhou Province