Olefination with Sulfonyl Halides and Esters: Synthesis of Unsaturated Sulfonyl Fluorides

Abstract

Methanedisulfonyl fluoride, CH 2 (SO 2 F) 2 , transforms aromatic aldehydes into β-arylethenesulfonyl fluorides, useful substrates for the SuFEx “click”-type transformations. The reaction mimics mechanism of the Horner–Wadsworth–Emmons olefination, which runs via addition of the carbanion, followed by cyclization–fragmentation of the four-membered ring intermediate. In the absence of base, electron-rich aldehydes follow an alternative pathway of the Knoevenagel condensation to provide unsaturated 1,1-disulfonyl fluorides. We demonstrate also trapping of elusive ethene-1,1-disulfonyl fluoride, CH 2 =C(SO 2 F) 2 , with 4-(dimethylamino)pyridine (DMAP) that forms zwitterionic adduct, characterized with X-ray studies.

Chemoselective Reactions of Functionalized Sulfonyl Halides

“…In particular, base-mediated intra- [26] and intermolecular [152][153][154][155] alkylations (Scheme 18), as well as Knoevenagel-type condensations with aromatic aldehydes providing styryl [156] or α-halostyryl [121,123,157] sulfonyl fluorides should be mentioned (Scheme 19).…”

“…Due to its high electronegativity, the SO 2 F fragment of aliphatic sulfonyl fluorides increases CH acidity at the α position, which provides numerous possibilities for further electrophilic functionalization. In particular, base‐mediated intra‐ [26] and intermolecular [152–155] alkylations (Scheme 18), as well as Knoevenagel‐type condensations with aromatic aldehydes providing styryl [156] or α‐halostyryl [121,123,157] sulfonyl fluorides should be mentioned (Scheme 19).…”

Stereoselective Fluorosulfonylation of Vinylboronic Acids for (E)-Vinyl Sulfonyl Fluorides with Copper Participation

“…The vinyl sulfonyl fluorides (vinyl-SO 2 F) have been synthesized straightforwardly through metal-catalyzed coupling reactions of ethenesulfonyl fluoride (ESF) with aryl iodides by Sharpless, boronic acids by Arvidsson and Qin, and diazonium salts by Wu or via a C–H activation strategy by Qin and Yu . Using methanedisulfonyl fluoride by Barbasiewicz or ethyl diethylphosphoryl methanesulfonate by Liskamp, electron-rich aldehydes have been converted into β-aryl or alkyl vinyl sulfonyl fluorides. The free radical fluorosulfonylation of olefins or alkynes provides an efficient method for the synthesis of various sulfonyl fluorides .…”

Ethene‐1,1‐disulfonyl Difluoride (EDSF) for SuFEx Click Chemistry: Synthesis of SuFExable 1,1‐Bissulfonylfluoride Substituted Cyclobutene Hubs

“…[29][30][31] The fluorosulfuryl isocyanate (FSI) and methanedisulfonyl fluoride (MDSF) reagents represent the latest additions to the SuFEx family, facilitating the synthesis of fluorosulfuryl carbamates (and ureas) and unsaturated 1,1disulfonyl fluorides, respectively. [32,33] Building on our previous work in developing α,β-unsaturated SuFEx hubs (BESF, SASF), we present ethene-1,1-disulfonyl difluoride (EDSF), an unprecedented SuFEx reagent for the synthesis of SuFExable 1,1-bissulfonylfluoride substituted cyclobutene hubs.…”