Synthesis of -Tosyloxylated gem-Difluoroalkanes via Elusive [2,3]-Sulfonyloxy Migration

29 April 2022, Version 3
This content is a preprint and has not undergone peer review at the time of posting.


gem-Difluoroalkanes widely exist in pharmaceuticals, agrochemicals and materials. Reported herein is a facile synthesis of tosyloxylated gem-difluoroalkanes via an oxidative fluorination of readily available vinyl sulfonates. An intriguing [2,3]-sulfonyloxy migration, which has been rarely known, is involved as a key step. The OTs group within the products enables a divergent and modular synthesis of a wide variety of functionalized gem-difluoroalkanes via simple and reliable SN2 reactions. Notable features of this protocol include mild reaction conditions, high efficiency and remarkably good functional group tolerance. Theoretical mechanistic studies were conducted, supporting a rate-determining [2,3]-sulfonyloxy shift is involved.


[2 3]-sulfonyloxy migration
vinyl sulfonate
hypervalent iodine
late-stage modification

Supplementary materials

supporting information
General information, experimental procedures, new com-pound characterization, DFT calculation detail, spectroscopic data, and NMR spectra.


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