Journal ArticleDOI
Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry
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TLDR
It is shown that proton or silicon centers can activate the exchange of S�F bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis.Abstract:
Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of organic chemists as the most commonly used S(VI) electrophiles, and the parent sulfuryl chloride, O2 S(VI) Cl2 , has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the S(VI) Cl bond is exceedingly sensitive to reductive collapse yielding S(IV) species and Cl(-) . Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2 -F and SO2 F2 ) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here we seek to revive it, along with John Hyatt's unnoticed 1979 full paper exposition on CH2 CH-SO2 -F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2 F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed.read more
Citations
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Emerging and Re-Emerging Warheads for Targeted Covalent Inhibitors: Applications in Medicinal Chemistry and Chemical Biology
Matthias Gehringer,Stefan Laufer +1 more
TL;DR: An overview of warheads-beyond α,β-unsaturated amides-recently used in the design of targeted covalent ligands is provided, with special emphasis on the discussion of reactivity and of case studies illustrating applications in medicinal chemistry and chemical biology.
Journal ArticleDOI
Sulfonyl fluorides as privileged warheads in chemical biology
Arjun Narayanan,Lyn H. Jones +1 more
TL;DR: The use of sulfonyl fluoride probes in chemical biology is reviewed and three new probes are introduced that provide new insights into the mechanism behind the formation of fluoride in seawater.
Journal ArticleDOI
50th Anniversary Perspective: Polymer Functionalization
Eva Blasco,Michael B. Sims,Anja S. Goldmann,Anja S. Goldmann,Brent S. Sumerlin,Christopher Barner-Kowollik,Christopher Barner-Kowollik +6 more
TL;DR: The translation of small molecule chemistries into efficient methodologies for polymer functionalization spans several decades, enabling critical advances in soft matter materials synthesis with tailored and adaptive property profiles.
Journal ArticleDOI
The growing applications of SuFEx click chemistry
TL;DR: This review discusses the growing number of applications of SuFEx, which can be found in nearly all areas of modern chemistry; from drug discovery to materials science.
Journal ArticleDOI
Broad-Spectrum Kinase Profiling in Live Cells with Lysine-Targeted Sulfonyl Fluoride Probes
Q Zhao,Xiaohu Ouyang,Xiaobo Wan,Ketan S. Gajiwala,John Charles Kath,Lyn H. Jones,Alma L. Burlingame,Jack Taunton +7 more
TL;DR: The design of sulfonyl fluoride probes that covalently label a broad swath of the intracellular kinome with high efficiency are reported, highlighting the utility of lysine-targeted sulfonyL fluoride probes in demanding chemoproteomic applications.
References
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Journal ArticleDOI
Synthesis and porcine pancreatic elastase inhibitory evaluation of 6α-(sulfonyl)oxy-and 6α-chloropenicillanate sulfone esters and 3α-(acyloxy)methyl-6α-chloropenam sulfones
Carlos E. Boschetti,Ernesto G. Mata,Oreste A. Mascaretti,Julia A. Cricco,Gabriela Coux,Oscar A. Roveri +5 more
TL;DR: In this article, the synthesis of 6α-chloropenicillanate sulfone esters 4a-c, 9, the acetate and benzoate of 3α-hydroxymethyl-6α -chloropenam sulfones 6a-b and pivaloyloxymethyl and benzyl esters of several 6α-(sulfonyl)oxypenicillaneate sulfones 12, 15a1-a3, 15b1-b3 and 15b 1-b2 are reported.
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Vinylfluorosulfonates - preparation and reactivity
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Fluorsulfonsäure als Reaktionsmedium und Fluorierungsmittel in der anorganischen Chemie
TL;DR: Fluorsulfonsaure, HSO3F, is in wasriger Losung und als wasserfreie Substanz bekannt as mentioned in this paper, leitet den elektrischen Strom, was auf eine Eigendissoziation schliesen last.
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Contributions to the Development of New Substitution Patterns of Penicillins: Synthesis of New Penicillins Derivatives and Evaluation of their Porcine Pancreatic Elastase Inhibitory Activity
Carlos E. Boschetti,Ernesto G. Mata,Oreste A. Mascaretti,Julia A. Cricco,Gabriela Coux,Anabella F. Lodeyro,Oscar A. Roveri +6 more
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