Photoredox-catalyzed aminofluorosulfonylation of unactivated olefins

Zhong, Tao; Yi, Ji-Tao; Chen, Zhida; Zhuang, Quan-Can; Li, Yong-Zhao; Lu, Gui; Weng, Jiang

doi:10.1039/d1sc02503a

Cited by 63 publications

(25 citation statements)

References 82 publications

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“…Very recently, benzimidazolium-based reagents (Figure A) were simultaneously uncovered by Wang and Liao , group independently to serve as sulfonyl fluoride radical precursors by photoredox catalysis, enabling the synthesis of alkenyl sulfonyl fluorides and β-alkoxy sulfonyl fluorides, among other functionalities. Weng and co-workers formed carbon-centered radicals by proton-coupled electron transfer (PCET) to amides and intramolecular 5- exo -trig cyclization with alkenes or by energy transfer (EnT)-mediated decarboxylation of oxime esters . These can then be trapped by SO 2 and “F + ” equivalents to enable the intramolecular 1,2-amido-fluorosulfonylation of alkenes and decarboxylative fluorosulfonylation of oxime esters, respectively.…”

Section: Introductionmentioning

confidence: 99%

EnT-Mediated N–S Bond Homolysis of a Bifunctional Reagent Leading to Aliphatic Sulfonyl Fluorides

et al. 2023

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Sulfur(VI) fluoride exchange (SuFEx) gives rise to a plethora of high-valent sulfur linkages; however, the availability of (aliphatic) sulfonyl fluoride manifolds lag behind, owing to the limited sources of introducing the SO2F moiety via a classical two-electron approach. Recently, radical-based methodologies have emerged as a complementary strategy to increase the diversity of accessible click partners. In this work, synthesis of a bench-stable sulfamoyl fluoride reagent is presented, which may undergo sigma-bond homolysis upon visible-light-induced sensitization to form protected β-amino sulfonyl fluorides from alkene feedstocks. Notably, this offers an appealing strategy to access various building blocks for peptido sulfonyl fluorides, relevant in a medicinal chemistry context, as well as an intriguing entry to β-ammonium sulfonates and β-sultams, from alkenes. Densely functionalized 1,3-sultones were obtained by employing allyl alcohols as substrates. Surprisingly, allyl chloride-derived β-imino sulfonyl fluoride underwent S–O bond formation and ring closure to yield rigid cyclopropyl β-imino sulfonate ester under SuFEx conditions. Furthermore, by engaging a thiol-based hydrogen atom donor in the reaction, the reactivity of the same reagent can be tuned toward the direct synthesis of aliphatic sulfonyl fluorides. Mechanistic experiments indicate an energy transfer (EnT)-mediated process. The transient sulfonyl fluoride radical adds to the alkene and product formation occurs upon either radical–radical coupling or hydrogen atom transfer (HAT), respectively.

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Section: Introductionmentioning

confidence: 99%

EnT-Mediated N–S Bond Homolysis of a Bifunctional Reagent Leading to Aliphatic Sulfonyl Fluorides

et al. 2023

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“…With the ability to synthesize pyrrolidinone-, oxazolidinone-, and imidazolidinone-containing sulfonyl fluorides, Zhong et al reported a straightforward strategy to form aliphatic sulfonyl fluorides in a multicomponent approach. 308 A PCET mechanism is responsible for the generation of an amidyl radical that initiates the 5-exo-trig cyclization. DABSO and N-fluorobenzenesulfonimide (NFSI) are respectively the SO 2 surrogate and the fluorine source.…”

Section: Miscellaneousmentioning

confidence: 99%

Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

et al. 2022

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“…Sulfonyl fluorides as the most widely used connective hubs of SuFEx click reaction have attracted enormous attention and find widespread applications in the fields of chemical biology 2 – 6 , drug discovery 7 – 11 and materials science 12 – 16 . Methods have been developed for rapid construction of sulfonyl fluoride moiety, including the chloride-fluoride exchange of sulfonyl chlorides 17 – 19 , SO 2 insertion/fluorination 20 – 23 , electrophilic fluorination of thiols and anodic oxidative fluorination 24 – 27 . Compared with the above mentioned S-F bond formation, direct fluorosulfonylation would provide a concise and redox economic approach for C-SO 2 F bond formation.…”

Section: Introductionmentioning

confidence: 99%

A practical fluorosulfonylating platform via photocatalytic imidazolium-based SO2F radical reagent

Zhang

et al. 2022

Nat Commun

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Sulfonyl fluorides are key components in the fields of chemical biology, materials science and drug discovery. In this line, the highly active SO2F radical has been employed for the construction of sulfonyl fluorides, but the utilization of gaseous ClSO2F as radical precursor is limited due to the tedious and hazardous preparation. Meanwhile, the synthesis of sulfonyl fluorides from inert SO2F2 gas through a fluorosulfonyl radical (·SO2F) process has met with inevitable difficulties due to the high homolytic bond dissociation energy of the S(VI)-F bond. Here we report a radical fluorosulfonylation strategy for the stereoselective synthesis of alkenyl sulfonyl fluorides and functional alkyl sulfonyl fluorides with an air-stable crystalline benzimidazolium fluorosulfonate cationic salt reagent. This bench-stable redox-active reagent offers a useful and operational protocol for the radical fluorosulfonylation of unsaturated hydrocarbons with good yield and high stereoselectivity, which can be further transformed into valuable functional SO2F moieties.

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Photoredox-catalyzed aminofluorosulfonylation of unactivated olefins

Abstract: The development of efficient approaches to access sulfonyl fluorides is of great significance because of the widespread applications of this structural motif in many areas, among which the emerging Sulfur...

Cited by 63 publications

References 82 publications

EnT-Mediated N–S Bond Homolysis of a Bifunctional Reagent Leading to Aliphatic Sulfonyl Fluorides

EnT-Mediated N–S Bond Homolysis of a Bifunctional Reagent Leading to Aliphatic Sulfonyl Fluorides

Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

A practical fluorosulfonylating platform via photocatalytic imidazolium-based SO2F radical reagent

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