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
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Journal ArticleDOI
Radical Fluorosulfonylation: Accessing Alkenyl Sulfonyl Fluorides from Alkenes
TL;DR: The development of the first radical fluorosulfonylation of alkenes based on FSO2 radicals generated under photoredox conditions is reported, providing a new and general access to alkenyl sulfonyl fluorides, including structures that would otherwise be challenging to synthesize with previously established cross coupling methods.
Journal ArticleDOI
A Rh-Catalyzed Air and Moisture Tolerable Aldehyde (Ketone)-Directed Fluorosulfonylvinylation of Aryl C(sp2)–H Bonds
Chen Li,Shi-Meng Wang,Hua-Li Qin +2 more
TL;DR: The first Rh-catalyzed activation of ortho sp2 C-H bonds of aldehydes (ketones) for monoselective coupling with ethenesulfonyl fluoride was accomplished without covalent or transient preinstallation of imines.
Journal ArticleDOI
Metal‐Free Synthesis of Functional 1‐Substituted‐1,2,3‐Triazoles from Ethenesulfonyl Fluoride and Organic Azides
Marie-Claire Giel,Christopher J. Smedley,Emily R. R. Mackie,Taijie Guo,Jiajia Dong,Tatiana P. Soares da Costa,John E. Moses +6 more
TL;DR: 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).
Journal ArticleDOI
Covalent Small Molecules as Enabling Platforms for Drug Discovery.
TL;DR: This review surveys the increasing number of drug discovery platforms employing covalent chemistries, and highlights the utility of these techniques for identifying and characterising small molecules and biological targets.
Journal ArticleDOI
Covalent Molecular Probes for Class A G Protein-Coupled Receptors: Advances and Applications
Dietmar Weichert,Peter Gmeiner +1 more
TL;DR: This work reviews covalently binding molecular probes for class A GPCRs with a focus on ligands comprising cross-linking groups that do not require photoactivation and further highlight their significant and diverse applications.
References
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Journal ArticleDOI
A stepwise huisgen cycloaddition process: copper(I)-catalyzed regioselective "ligation" of azides and terminal alkynes.
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Click Chemistry: Diverse Chemical Function from a Few Good Reactions.
TL;DR: In this paper, a set of powerful, highly reliable, and selective reactions for the rapid synthesis of useful new compounds and combinatorial libraries through heteroatom links (C-X-C), an approach called click chemistry is defined, enabled, and constrained by a handful of nearly perfect "springloaded" reactions.
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Peptidotriazoles on solid phase: [1,2,3]-triazoles by regiospecific copper(i)-catalyzed 1,3-dipolar cycloadditions of terminal alkynes to azides.
TL;DR: A novel regiospecific copper(I)-catalyzed 1,3-dipolar cycloaddition of terminal alkynes to azides on solid-phase is reported, and the X-ray structure of 2-azido-2-methylpropanoic acid has been solved, to yield structural information on the 1, 3-dipoles entering the reaction.
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1,3-Dipolar Cycloadditions. Past and Future†
TL;DR: In contrast to the very large number of special methods applicable to syntheses in the heterocyclic series, relatively few general methods are available as discussed by the authors, and the 1,3-dipolar addition offers a remarkably wide range of utility in the synthesis of five-membered heterocycles.
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A Strain-Promoted [3 + 2] Azide−Alkyne Cycloaddition for Covalent Modification of Biomolecules in Living Systems
TL;DR: A strain-promoted [3 + 2] cycloaddition between cyclooctynes and azides that proceeds under physiological conditions without the need for a catalyst was demonstrated by selective modification of biomolecules in vitro and on living cells, with no apparent toxicity.