Fluorodesulfurization of aliphatic orthothioesters

Abstract

In contrast with aromatic orthothio esters that undergo desulfurative fluorination to produce trifluoromethyl substituted aromatics, aliphatic orthothio esters react with BrF with replacement of only one or two methylthio groups by fluorine. An elimination step often follows the first sulfur replacement to produce novel unsaturated fluorinated systems. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 31–34, 1999

Fluoro-Pummerer rearrangement and analogous reactions

“…The reaction of the 3-hydroxy-3-phenyltrithio orthoester (198) (formed from corresponding epoxides and the lithium salt of trithio orthoformiate) with DBH and Olah's reagent led to stepwise replacement of one (199) or two methylthio groups by fluoride (200) (Scheme 71) [150].…”

Fluorination of Thiocarbonyl Compounds with Bis(2-methoxyethyl)aminosulfur Trifluoride (Deoxo-Fluor Reagent): A Facile Synthesis of gem-Difluorides

“…Alternative methods involve the reaction of carbonyl-derived hydrazones and diazo compounds with the strong oxidative fluorinators, iodine monofluoride or fluorine. gem -Difluorides can also be prepared by the oxidative desulfurization−fluorination of ortho thioesters, dithiolanes, and thiocarbonyl derivatives with electrophilic halonium species in the presence of fluoride ions is the only report of a thiocarbonyl to gem -difluoride conversion using aminosulfur trifluorides.…”