A Heck–Matsuda Process for the Synthesis of β‐Arylethenesulfonyl Fluorides: Selectively Addressable Bis‐electrophiles for SuFEx Click Chemistry

Qin, Hua‐Li; Zheng, Qinheng; Bare, Grant A. L.; Wu, Peng; Sharpless, K. Barry

doi:10.1002/ange.201608807

Cited by 48 publications

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“…There are several examples of Heck-type cross-couplings with aryl halides 61 , 62 or boronic acids, 63 , 64 and vinyl fluorides. Interestingly, there are also mechanistically distinct photocatalytic examples reported.…”

Section: Catalytic Syntheses Of Sulfur(vi) Fluoridesmentioning

confidence: 99%

The Emerging Applications of Sulfur(VI) Fluorides in Catalysis

et al. 2021

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Section: Catalytic Syntheses Of Sulfur(vi) Fluoridesmentioning

confidence: 99%

The Emerging Applications of Sulfur(VI) Fluorides in Catalysis

et al. 2021

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“…Substrates with electron donating substituents on the aryl ring gave little to no product formation under these conditions; this is in accordance with studies by Qin et al , who concluded that the Michael reaction of secondary amines on β-arylethenesulfonyl fluorides required EWG on the aryl group when performed in THF or DCM. 26 Further, the electron withdrawing fluoro substituent on the phenyl ring of 4 was evaluated and compound 6g was isolated in 80% yield using aniline as the amine of choice. All structures of compounds appearing in Scheme 2 was unequivocally deduced from full spectroscopic characterization.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of novel 1,2,4-thiadiazinane 1,1-dioxidesviathree component SuFEx type reaction

et al. 2018

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Herein, we report the preparation of 1,2,4-thiadiazinane 1,1-dioxides from reaction of b-aminoethane sulfonamides with dichloromethane, dibromomethane and formaldehyde as methylene donors. The baminoethane sulfonamides were obtained through sequential Michael addition of amines to a,bunsaturated ethenesulfonyl fluorides followed by further DBU mediated sulfur(VI) fluoride exchange (SuFEx) reaction with amines at the S-F bond.Scheme 3 Formation of 1,2,4-thiadiazinane 1,1-dioxides under onepot conditions in DCM or using a two-step procedure with other methylene donors for cyclization. a (One pot) 10 equiv. amine, 50 mol% DBU, 5.0 ml DCM, reflux; b b-aminoethane sulfonamide, 20 mol% DBU, 5 ml DCM, reflux; c b-aminoethane sulfonamide, cat. acetic acid, 1.1 equiv. CH 2 O, 3 ml EtOH or MeOH microwave 90 C, 200 W, 5 min; d baminoethane sulfonamide, 20 mol% DBU, 5 ml DBM, reflux. Note for b-d, the yield refers to the final step.This journal is

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“…Zuschriften 4928 www.angewandte.de arylethenesulfonyl fluorides were obtained in either similar or better yields than those obtained by ap reviously described Heck-Matsuda protocol. [7] It is notable that ap henolic hydroxy group (3p, 3x, 3ac,a nd 3ag)i sw ell tolerated in this process,a nd was incompatible in the Heck-Matsuda process.N ot surprisingly,t he catalytic system distinguished between iodide and other potential reactive halides (Br: 3h, 3t and Cl: 3g). Moreover,t his new protocol succeeded with the multivalent substrate,1 ,3-diiodobenzene (2aj), for the first time.1 ,3-Phenylene bis(ethenesulfonyl fluoride) (3aj) was obtained in excellent yield, and was readily scaled up to 10 mmol with the same outcome.T he resulting divalent compound was found applicable in aS uFEx poly(aryl vinylsulfonate) synthesis.…”

Section: Angewandte Chemiementioning

confidence: 93%

“…ESF,a mong the three irreplaceable scaffolds of SuFEx chemistry,i su nique for its versatile reactivity.W eh ave demonstrated ESF as an essential building block to prepare the otherwise difficult to access compounds,2-arylethenesulfonyl fluorides,t hrough aH eck-Matsuda process (Figure 1b1). [7] 2-Arylethenesulfonyl fluorides represent ar are family of selectively addressable bifunctional electrophiles. Sulfonyl fluorides and vinyl sulfonates (or sulfone) can be readily prepared from 2-arylethenesulfonyl fluorides by Michael addition and SuFEx, respectively,a nd both are important classes of electrophiles and potential covalent pharmacophores ( Figure 1c).…”

Section: Palladium-catalyzed Fluorosulfonylvinylation Of Organic Iodidesmentioning

confidence: 99%

Palladium‐Catalyzed Fluorosulfonylvinylation of Organic Iodides

et al. 2017

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A palladium-catalyzed fluorosulfonylvinylation reaction of organic iodides is described. Catalytic Pd(OAc) 2 with stoichiometric silver(I) trifluoroacetate enables the coupling process between an (hetero)aryl or alkenyl iodide and ethenesulfonyl fluoride (ESF, 1). The method is demonstrated in the successful syntheses of eighty-eight otherwise difficult to access compounds in up to 99% yields, including the unprecedented 2-heteroarylethenesulfonyl fluorides, and 1,3-dienylsulfonyl fluorides. FluorosulfonylvinylationCatalytic Pd(OAc) 2 with stoichiometric silver(I) trifluoroacetate enables the coupling process between an (hetero)aryl or alkenyl iodide and ethenesulfonyl fluoride. The method is demonstrated in the successful syntheses of eighty-eight otherwise difficult to access compounds in up to 99% yields, including the unprecedented 2-heteroarylethenesulfonyl fluorides, and 1,3-dienylsulfonyl fluorides.[+] These authors contributed equally.Supporting information for this article is given via a link at the end of the document. By employing three highly connective molecules, sulfuryl fluoride (SO 2 F 2 ), [1] thionyl tetrafluoride (O=SF 4 ), [2] and ethenesulfonyl fluoride (CH 2 =CH-SO 2 F, ESF, 1), [1], [3], [4] we are able to readily gain SuFEx-abilities for the compounds from nature's nucleophile pool or from the petrochemicals, and finally achieve functions in service of multiple disciplines [5], [6] via catalytic SuFEx protocols ( Figure 1a). Searching for new S VI -F functional groups and developing reliable methods for their installations are considered the major challenge for evolving the current SuFEx chemistry. HHS Public AccessESF, among the three irreplaceable scaffolds of SuFEx chemistry, is unique for its versatile reactivity. We have demonstrated ESF as an essential building block to prepare the otherwise difficult to access compounds, 2-arylethenesulfonyl fluorides, through a Heck-Matsuda process [ Figure 1b(1)]. [7] 2-Arylethenesulfonyl fluorides represent a rare family of selectively addressable bifunctional electrophiles. Sulfonyl fluorides and vinyl sulfonates (or sulfone) can be readily prepared from 2-arylethenesulfonyl fluorides, via Michael addition and SuFEx, respectively, which are both important classes of electrophiles and potential covalent pharmacophores ( Figure 1c). [8]-[10] The latter provide permanent inhibition of target proteins, which is of special interest for us. [11] Among the 152 approved S VIcontaining drugs, [12] 96 (63%) of them are (hetero)aryl sulfonyl molecules [(Het)Ar-SO 2 -Q, including aryl sulfones, sulfonamides, sulfonic acids and sulfonate esters]. The vinylogous analogs [(Het)Ar-CH=CH-SO 2 -Q] are much less explored, but could be interesting. Rigosertib (Figure 1d), a Phase III drug candidate treating myelodisplastic syndrome, is first of this kind to show promising bioactivity. [13] It is reasonable to conclude from the above that general methods for the synthesis of 2-substituted ethenesulfonyl fluorides would open up access to a new and likely v...

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A Heck–Matsuda Process for the Synthesis of β‐Arylethenesulfonyl Fluorides: Selectively Addressable Bis‐electrophiles for SuFEx Click Chemistry

Cited by 48 publications

References 57 publications

The Emerging Applications of Sulfur(VI) Fluorides in Catalysis

The Emerging Applications of Sulfur(VI) Fluorides in Catalysis

Synthesis of novel 1,2,4-thiadiazinane 1,1-dioxidesviathree component SuFEx type reaction

Palladium‐Catalyzed Fluorosulfonylvinylation of Organic Iodides

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