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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Journal ArticleDOI
A cascade process for directly converting nitriles (RCN) to cyanamides (RNHCN) via SO2F2-activated Tiemann rearrangement
TL;DR: A simple, mild and practical process for the direct conversion of nitriles to cyanamides was newly discovered and exhibited a wide substrate scope as well as great functional group-tolerability.
Journal ArticleDOI
Rapid Access to N-Protected Sulfonimidoyl Fluorides: Divergent Synthesis of Sulfonamides and Sulfonimidamides.
TL;DR: In this article, a copper-catalyzed approach for the conversion of various arenediazonium salts to the corresponding N-protected sulfonimidoyl fluorides is presented.
Journal ArticleDOI
Synthesis of N-Acyl Sulfamates from Fluorosulfates and Amides
Philippe Gilles,Cedrick Veryser,Sarah Vangrunderbeeck,Sam Ceusters,Luc Van Meervelt,Wim M. De Borggraeve +5 more
TL;DR: A novel synthetic strategy toward N-acyl sulfamates was developed, using fluorosulfates, a new emerging class of electrophiles, to construct the sulfamate core, which precludes handling of chlorosulfonyl isocyanate and sulfamoyl chloride.
Journal ArticleDOI
Sulfur (VI) Fluoride Exchange Polymerization for Large Conjugate Chromophores and Functional Main-Chain Polysulfates with Nonvolatile Memory Performance
TL;DR: In this work, four functional main-chain polysulfates are synthesized in high yield using the SuFEx reaction at room temperature to provide a feasible and efficient synthetic methodology for the preparation of new memory materials.
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.