A Unified Strategy for Arylsulfur(VI) Fluorides from Aryl Halides: Access to Ar‐SOF₃ Compounds

Abstract

A convenient protocol to selectively access various arylsulfur(VI) fluorides from commercially available aryl halides in a divergent fashion is presented. Firstly, a novel sulfenylation reaction with the electrophilic N‐(chlorothio)phthalimide (Cl‐S‐Phth) and arylzinc reagents afforded the corresponding Ar‐S‐Phth compounds. Subsequently, the S(II) atom was selectively oxidized to distinct fluorinated sulfur(VI) compounds under mild conditions. Slight modifications on the oxidation protocol permit the chemoselective installation of 1, 3, or 4 fluorine atoms at the S(VI) center, affording the corresponding Ar‐SO2F, Ar‐SOF3, and Ar‐SF4Cl. Of notice, this strategy enables the effective introduction of the rare and underexplored ‐SOF3 moiety into various (hetero)aryl groups. Reactivity studies demonstrate that such elusive Ar‐SOF3 can be utilized as a linchpin for the synthesis of highly coveted aryl sulfonimidoyl fluorides (Ar‐SO(NR)F).

Electrochemical Synthesis of Sulfonyl Fluorides with Triethylamine Hydrofluoride

“…In addition to direct substitution of sulfonyl compounds with fluoride anion, oxidative fluorination has frequently been adopted, as has the use of sulfonyl precursors. For example, N ‐fluorobenzenesulfonimide, [ 13 ] Selectfluor, [ 14 ] and trichloroisocyanuric acid/KF [ 15 ] are well‐documented reagents for oxidative fluorination. Sulfuryl fluoride (SO 2 F 2 ) is a gaseous fluoride source that has been used with aryl organometallic reagents to prepare aromatic sulfonyl fluorides.…”

Recent advances in thiolation via sulfur electrophiles

“…In 2020, Cornella and co-workers developed a protocol to selectively access various arylsulfur(VI) fluorides from commercially available arylhalides (Scheme 53). 67…”

Recent Advances in the Synthesis and Medicinal Chemistry of SF5 and SF4Cl Compounds

“…Template for SYNTHESIS Thieme equiv., TFA 10 mol%) (Scheme 12). 16 Other fluorinated sulfur compounds -such as Ar-SO2F and Ar-SOF3 -were selectively obtained using less equiv. of TCICA and KF (see Table 1).…”