Aliphatic Sulfonyl Fluoride Synthesis via Fluoroalkylfluoro-sulfonylation of Unactivated Olefins under Photoredox and Palladium Dual Catalysis

doi:10.6023/cjoc202604031

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (10): 4119-4128.DOI: 10.6023/cjoc202604031 Previous Articles Next Articles

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光氧化还原/钯协同催化未活化烯烃氟烷基氟磺酰化合成脂肪族磺酰氟

彭莹莹^†, 张超艺^†, 伍雄, 刘忍, 庞婉, 马晓玉^*(), 刘超^*()

上海应用技术大学化工与能源技术学部上海绿色氟代制药工程技术研究中心上海绿色氟代制药工程技术研究中心上海 201418

收稿日期:2026-04-22 修回日期:2026-05-13 发布日期:2026-06-10
通讯作者: 马晓玉, 刘超
作者简介:
^†共同第一作者.
基金资助:
国家自然科学基金(22471172)

Aliphatic Sulfonyl Fluoride Synthesis via Fluoroalkylfluoro-sulfonylation of Unactivated Olefins under Photoredox and Palladium Dual Catalysis

Yingying Peng^†, Chaoyi Zhang^†, Xiong Wu, Ren Liu, Wan Pang, Xiaoyu Ma^*(), Chao Liu^*()

Faculty of Chemical and Energy Technology and Shanghai Engineering Research Center of Green Fluoropharmaceutical Technology, Shanghai Institute of Technology, Shanghai 201418

Received:2026-04-22 Revised:2026-05-13 Published:2026-06-10
Contact: Xiaoyu Ma, Chao Liu
About author:
^†These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22471172)

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Abstract

Both fluoroalkyl and fluorosulfonyl groups are important structural motifs in bioactive molecules and valuable functional units in synthetic chemistry. Herein, a photoredox-and palladium-dual-catalyzed fluoroalkylfluorosulfonylation of unactivated olefins was reported using aryl trifluoromethyl compounds as fluoroalkyl radical precursors, 1,4-diazabicyclo-[2.2.2]octane-bis(sulfur dioxide) adduct (DABSO) as the sulfur dioxide source, and N-fluorobenzenesulfonimide (NFSI) as the fluorine source via radical sulfur dioxide insertion and fluorination strategy. This transformation enables the simultaneous installation of fluoroalkyl and fluorosulfonyl groups across carbon-carbon double bonds in a single step, thus providing an efficient and concise approach to structurally diverse aliphatic sulfonyl fluorides. The reaction proceeds under mild conditions and exhibits good functional-group tolerance. Furthermore, the resulting sulfonyl fluoride products can be readily transformed into valuable compounds through SuFEx reactions.

Key words: fluoroalkylfluorosulfonylation, sulfonyl fluorides, alkene difunctionalization, photoredox/palladium dual catalysis

Cite this article

Yingying Peng, Chaoyi Zhang, Xiong Wu, Ren Liu, Wan Pang, Xiaoyu Ma, Chao Liu. Aliphatic Sulfonyl Fluoride Synthesis via Fluoroalkylfluoro-sulfonylation of Unactivated Olefins under Photoredox and Palladium Dual Catalysis[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4119-4128.

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References 16

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Entry	Variation from standard conditions	Yield^b/%
1	None	76
2	No H₂O	n.d.
3	DCM, DCE, PE, or toluene instead of THF	n.d.
4	MeCN, DMF, or NMP instead of THF	n.d.
5	Na₂S₂O₄, K₂S₂O₅, SO₂ aq. thiourea dioxide instead of DABSO	n.d.
6	Selectfluor intead of NFSI	73
7	Pd(t-Bu₂PPh)₂Cl₂ or Pd(PPh₃)₄ instead of Pd(PhCN)₂Cl₂	<50
8	Cu, Mn intead of Zn	n.d.
9	1.0 equiv. of K₃PO₄	10
10	2.0 equiv. of K₃PO₄	30
11	No K₃PO₄	47
12	No Pd(PhCN)₂Cl₂	n.d.
13	No Xantphos	n.d.
14	No light	n.d.

Entry	Variation from standard conditions	Yield^b/%
1	None	76
2	No H₂O	n.d.
3	DCM, DCE, PE, or toluene instead of THF	n.d.
4	MeCN, DMF, or NMP instead of THF	n.d.
5	Na₂S₂O₄, K₂S₂O₅, SO₂ aq. thiourea dioxide instead of DABSO	n.d.
6	Selectfluor intead of NFSI	73
7	Pd(t-Bu₂PPh)₂Cl₂ or Pd(PPh₃)₄ instead of Pd(PhCN)₂Cl₂	<50
8	Cu, Mn intead of Zn	n.d.
9	1.0 equiv. of K₃PO₄	10
10	2.0 equiv. of K₃PO₄	30
11	No K₃PO₄	47
12	No Pd(PhCN)₂Cl₂	n.d.
13	No Xantphos	n.d.
14	No light	n.d.

光氧化还原/钯协同催化未活化烯烃氟烷基氟磺酰化合成脂肪族磺酰氟

Aliphatic Sulfonyl Fluoride Synthesis via Fluoroalkylfluoro-sulfonylation of Unactivated Olefins under Photoredox and Palladium Dual Catalysis

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