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Turning sulfonyl and sulfonimidoyl fluoride electrophiles into sulfur(VI) radicals for alkene ligation.

ABSTRACT: Sulfonyl and sulfonimidoyl fluorides are versatile substrates in organic synthesis and medicinal chemistry. However, they have been exclusively used as S(VI)⁺ electrophiles for defluorinative ligations. Converting sulfonyl and sulfonimidoyl fluorides to S(VI) radicals is challenging and underexplored due to the strong bond dissociation energy of S^VI-F and high reduction potentials, but once achieved would enable dramatically expanded synthetic utility and downstream applications. In this report, we disclose a general platform to address this issue through cooperative organosuperbase activation and photoredox catalysis. Vinyl sulfones and sulfoximines are obtained with excellent E selectivity under mild conditions by coupling reactions with alkenes. The synthetic utility of this method in the preparation of functional polymers and dyes is also demonstrated.

SUBMITTER: Wu X

PROVIDER: S-EPMC10449886 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

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Turning sulfonyl and sulfonimidoyl fluoride electrophiles into sulfur(VI) radicals for alkene ligation.

Wu Xing X Zhang Wenbo W Sun Guangwu G Zou Xi X Sang Xiaoru X He Yongmin Y Gao Bing B

Nature communications 20230824 1

Sulfonyl and sulfonimidoyl fluorides are versatile substrates in organic synthesis and medicinal chemistry. However, they have been exclusively used as S(VI)<sup>+</sup> electrophiles for defluorinative ligations. Converting sulfonyl and sulfonimidoyl fluorides to S(VI) radicals is challenging and underexplored due to the strong bond dissociation energy of S<sup>VI</sup>-F and high reduction potentials, but once achieved would enable dramatically expanded synthetic utility and downstream applica ...[more]

PMID: 37620301

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