Synthesis of bromodifluoromethyl phenyl sulfide, sulfoxide and sulfone [1]

Fluorinated Carbenes

“…Phenoxides, thiophenoxides, and thiolates behave similarly. 212,217,218 The reaction of difluorocarbene, generated from difluorodiazirine, and alcohols or acids produces difluoromethyl esters and difluoromethyl ethers, respectively (eq 45). 219 An interesting reaction was reported between difluorocarbene and an imine.…”

“…In related transformations, stabilized carbanions such as lithium acetylides (eq 44) , or malonates , undergo reaction with dibromodifluoromethane to form bromodifluoromethyl derivatives by an ionic chain mechanism involving difluorocarbene (Scheme ). Phenoxides, thiophenoxides, and thiolates behave similarly. ,,

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Friedel–Crafts‐Type Alkylation with Bromodifluoro(phenylsulfanyl)methane through α‐Fluorocarbocations: Syntheses of Thioesters, Benzophenones and Xanthones

“…The mesomeric interaction of unshared electron pairs of fluorine atoms (1aЈ) together with those of the phenylsulfanyl moiety (1aЈЈ) would increase the stability of the carbocation intermediate (Scheme 1). [9,10] Scheme 1.…”

Nucleophilic, radical, and electrophilic (phenylsulfonyl)difluoromethylations

“…Bromodifluoromethyl phenyl sulfone (PhSO 2 CF 2 Br, 2) was first reported by Burton and Wiemers [46], but the reports on its synthetic utility are rare [19,47]. Inspired by Dolbier's work that tetrakis(dimethylamino)ethylene (TDAE) can act as an efficient reducing agent to generate substituted difluoromethylated carbanions from halo-difluoromethyl precursors [48], Prakash et al have used PhSO 2 CF 2 Br/TDAE combination as a nucleophilic (phenylsulfonyl)difluoromethylation reagent (Scheme 16) [47].…”