The preparation of .beta.-fluoro thioethers

Abstract

Addition of benzenesulfenyl chloride to electron-rich olefins in the presence of silver produces /3-fluoro thioethers. The trans adducts could also be prepared from d-chloro thioethers and silver fluoride.

Electrochemistry Enabled Selective Vicinal Fluorosulfenylation and Fluorosulfoxidation of Alkenes

“…With the optimal reaction conditions determined, we first evaluated the scope of the electrochemical fluorosulfenylation of alkenes (Table 2). This reaction accommodated a wide array of para-, meta-, and orthosubstituted styrenes (5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17). Additionally, alkyl (18)(19)(20)(21), benzyl (22), pyridyl (23), and cycloalkyl (24-27) αsubstituted styrenes were all found to be well tolerated.…”

“…Typically, the vicinal fluorosulfenylation of alkenes is achieved by the reaction of alkenes with a chemically [11][12][13][14][15][16][17] or electrochemically 18 generated electrophilic thiolating agent ("RS +" ) to form an episulfonium ion 19 followed by nucleophilic fluorination (Scheme 1B). Such a polar approach, however, is limited by the requisite preparation of highly reactive and toxic thiolating agents.…”

New Sulfenyl Chloride Chemistry: Synthesis, Reactions and Mechanisms toward Carbon-Carbon Double Bonds

“…Cyclic olefins such as 1,2-diphenylcyclohexene (63), 1,2-diphenylcyclobutene (64), 1,4-dimethylcyclohexene (65), (1R)-(þ)--pinene (66), (1S)-(À)--pinene (67), 3-carene (68), camphene (69), 3,4-dihydro-2H-pyran (70), 2,5-dihydrofuran (71) and 2,5-dimethoxy-2,5-dihydrofuran (72) did not react with the series of sulfenyl chlorides. Acyclic olefins such as 1,1,2,2-tetramethylethylene (73), 1,1,2,2-tetraphenylethylene (74), 1,1,2,2-tetracyanoethylene (75), trans-stilbene (76), cis-stilbene (77), 1-bromo-2-methylpropene (78), styrene (79), bromostyrene (80) and vinylcyclohexane (81) were also tried [84]. We discovered [84] that these olefins 63-81 remained unaffected even if the reactions were carried out over a few weeks.…”

“…Purrington and Correa [80] proposed another way to obtain -fluoroalkylphenyl thioethers by the action of phenylsulfenyl chloride on an olefin in the presence of silver fluoride in acetonitrile solution.…”

Electronegativity Effects in Organic Synthesis: Differences in stability of isomeric substituted alkanes

“…This means that selectivity can be very high, and is a clear advantage of these oxygenated compounds over the corresponding chlorides. Fluorine is even more electronegative than oxygen, so it would be interesting to study isomerizations involving it, for example, the still undescribed [24] equilibria of P-thioalkyl fluorides [25].…”