Ethenesulfonyl Fluoride: The Most Perfect Michael Acceptor Ever Found?

Chen, Quan; Mayer, Péter; Mayr, Herbert

doi:10.1002/anie.201601875

Cited by 90 publications

(80 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In a competition experiment between equimolar amounts of β‐(4‐nitrophenyl)ethenesulfonyl fluoride ( 3 j ), a relatively robust compound within the β‐arylethenesulfonyl fluoride family, and ESF in the presence of 0.05 equivalents of a secondary amine, 1‐phenyl piperazine, we observed 100 % conversion and selectivity to the ESF‐Michael product ( 6 ) via 1 H NMR, without any detectable formation of 5 a (Scheme ). This result is qualitatively consistent with Mayr's recent discovery that 2‐phenylethenesulfonyl fluoride ( 3 a ) has an electrophilic reactivity 4.5 orders of magnitude lower than that of ESF in the context of Michael additions with sulfonium and pyridinium ylides …”

Section: Methodssupporting

confidence: 90%

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

et al. 2016

View full text Add to dashboard Cite

AH eck-Matsuda process for the synthesis of the otherwise difficult to access compounds, b-arylethenesulfonyl fluorides,i sd escribed. Ethenesulfonyl fluoride (i.e., vinylsulfonyl fluoride,o rE SF) undergoes b-arylation with stable and readily prepared arenediazonium tetrafluoroborates in the presence of the catalyst palladium(II) acetate to affordt he Eisomer sulfonyl analogues of cinnamoyl fluoride in 43-97 % yield. The b-arylethenesulfonyl fluorides are found to be selectively addressable bis-electrophiles for sulfur(VI) fluoride exchange (SuFEx) clickc hemistry,inwhich either the alkenyl moiety or the sulfonyl fluoride group can be the exclusive site of nucleophilic attack under defined conditions,m aking these rather simple cores attractive for covalent drug discovery.

show abstract

Section: Methodssupporting

confidence: 90%

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

et al. 2016

View full text Add to dashboard Cite

show abstract

“…[14-15] In fact, the reactions of ESF with a variety of nucleophiles are excellent approaches to produce alkyl sulfonyl fluorides. [10, 14, 15h] To produce polysulfonates with excellent repeating units variability, we chose ESF-amine/aniline adducts (i.e., bis-functionalized alkylsulfonyl fluorides) as AA monomers to react with bisphenol bis( t -butyldimethylsilyl) ethers (BB monomers) based on the following considerations: (1) amines, anilines and bisphenols are readily availability from commercial sources; (2) bis-functionalized and multi-functionalized amines and anilines have been wide applied in polymer science. [16] …”

mentioning

confidence: 99%

“…Reaction at 50 °C overnight afforded the corresponding products in near quantitative yields (Figure 1). It should be noted that by using our recently developed interphase, kilogram-scale ESF synthesis technique, [15f] amine/aniline ESF adducts (i.e., AA monomers) can be reliably prepared in hundred-gram scale quantities. On the other hand, the synthesis of bisphenol bis( t -butyldimethylsilyl) ethers (BB monomers) is accomplished by reacting t -butyldimethylsilyl chloride with bisphenols.…”

mentioning

confidence: 99%

SuFEx‐Based Polysulfonate Formation from Ethenesulfonyl Fluoride–Amine Adducts

et al. 2017

View full text Add to dashboard Cite

In this work, we describe the SuFEx-based polycondensation between bisalkylsulfonyl fluorides (AA monomers) and bisphenol bis(t-butyldimethylsilyl) ethers (BB monomers) using [Ph3P=N-PPh3]+[HF2]− as the catalyst. The AA monomers were prepared via the highly reliable Michael addition of ethenesulfonyl fluoride and amines/anilines while the BB monomers were obtained from silylation of bisphenols by t-butyldimethylsilyl chloride. With these reactions, we were able to achieve a remarkable diversity of monomeric building blocks by exploiting readily available amines, anilines, and bisphenols as starting materials. The SuFEx-based polysulfonate formation reaction exhibited excellent efficiency and functional group tolerance, producing polysulfonates with a variety of side chain functionalities in >99% conversion within 10 min to 1 h. When bearing an orthogonal group on the side chain, the polysulfonates can be further functionalized via click-chemistry based post-polymerization modification.

show abstract

“…[24,25] ESF offers many other advantages over ESCl in terms of stability and properties ( Figure 1C), [26] and has been described as "the most perfect Michael acceptor ever found". [24,27] Studies commenced by performing ar eaction between ESF and 6 following the method of Rondestvedt and Chang (cf.ESCl): [20] stirring in benzene at ambient temperature for 5 hours in as ealed tube.U nder these reaction conditions,n o products were observed and starting materials fully recovered. However,raising the reaction temperature to 100 8 8Cand stirring for af urther 5hours, 11 was isolated in 47 %y ield along with unreacted starting materials (see the Supporting Information).…”

mentioning

confidence: 99%

Metal‐Free Synthesis of Functional 1‐Substituted‐1,2,3‐Triazoles from Ethenesulfonyl Fluoride and Organic Azides

et al. 2019

View full text Add to dashboard Cite

The boom in growth of 1,4‐disubstituted triazole products, in particular, since the early 2000’s, can be largely attributed to the birth of click chemistry and the discovery of the CuI‐catalyzed azide–alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1‐substituted‐1,2,3‐triazoles has been surprisingly more challenging. Reported here is a straightforward and scalable click‐inspired protocol for the synthesis of 1‐substituted‐1,2,3‐triazoles from organic azides and the bench stable acetylene surrogate ethenesulfonyl fluoride (ESF). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal‐free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1‐substituted‐1,2,3‐triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1‐substituted triazolium sulfonyl fluoride salts.

show abstract

Ethenesulfonyl Fluoride: The Most Perfect Michael Acceptor Ever Found?

Cited by 90 publications

References 29 publications

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

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

SuFEx‐Based Polysulfonate Formation from Ethenesulfonyl Fluoride–Amine Adducts

Metal‐Free Synthesis of Functional 1‐Substituted‐1,2,3‐Triazoles from Ethenesulfonyl Fluoride and Organic Azides

Contact Info

Product

Resources

About