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

ABSTRACT: Methanedisulfonyl fluoride, CH₂(SO₂F)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, CH₂═C(SO₂F)₂, with 4-(dimethylamino)pyridine (DMAP) that forms zwitterionic adduct, characterized with X-ray studies.

SUBMITTER: Tryniszewski M

PROVIDER: S-EPMC9490844 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

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

Tryniszewski Michał M Basiak Dariusz D Barbasiewicz Michał M

Organic letters 20220602 23

Methanedisulfonyl fluoride, CH2(SO2F)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 condens ...[more]

PMID: 35653711

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