Journal ArticleDOI
Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry
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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Journal ArticleDOI
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
Click Chemistry In Situ: Acetylcholinesterase as a Reaction Vessel for the Selective Assembly of a Femtomolar Inhibitor from an Array of Building Blocks
Warren G. Lewis,Luke Green,Flavio Grynszpan,Zoran Radić,Paul R. Carlier,Palmer Taylor,M. G. Finn,K. Barry Sharpless +7 more
TL;DR: The generation of carbonic anhydrase inhibitors by using the SN2 reaction of a thiol with an -chloroketone in the presence of the enzyme target is described herein.
Journal ArticleDOI
Sulfonyl Fluorides as Inhibitors of Esterases. I. Rates of Reaction with Acetylcholinesterase, α-Chymotrypsin, and Trypsin
David Fahrney,Allen M. Gold +1 more
Journal ArticleDOI
Molecular Structure of Salt Solutions: A New View of the Interface with Implications for Heterogeneous Atmospheric Chemistry
TL;DR: In this article, the authors report results from molecular dynamics simulations of a series of sodium halide solution/air interfaces and develop a molecular picture of hydrogen bonding in the interfacial region that might be tested by surface sensitive spectroscopic experiments.
Journal ArticleDOI
On the Theory of Organic Catalysis "on Water"
Yousung Jung,Rudolph A. Marcus +1 more
TL;DR: In this article, a molecular origin of the striking rate increase observed in a reaction on water is studied theoretically, and a method is given for comparing the rate constants of different rate processes, homogeneous, neat and on-water, all of which have different units, by introducing models that reduce them to the same units.
Journal ArticleDOI
Molecular aspects of halide ion hydration: the cluster approach.
TL;DR: This review provides a historical context for the understanding of the hydration shell surrounding halide ions and illustrates how the cluster systems can be used, in combination with theory, to elucidate the behavior of water molecules in direct contact with the anion.