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
Sulfur–Fluoride Exchange (SuFEx)‐Mediated Synthesis of Sterically Hindered and Electron‐Deficient Secondary and Tertiary Amides via Acyl Fluoride Intermediates
Christopher J. Smedley,Andrew S. Barrow,Christian Spiteri,Marie-Claire Giel,Pallavi Sharma,John E. Moses +5 more
TL;DR: A new sulfur-fluoride exchange (SuFEx) click chemistry based protocol for the efficient amidation of carboxylic acids via acyl fluoride intermediates, which delivers challenging secondary and tertiary amides in excellent yields from sterically hindered and electron-deficient amines.
Patent
Tank-binding kinase inhibitor compounds
Zhimin Du,Guerrero Juan A,Joshua Kaplan,John E. Knox,Jennifer R. Lo,Scott A. Mitchell,Devan Naduthambi,Phillips Barton W,Chandrasekar Venkataramani,Peiyuan Wang,William J. Watkins,Zhongdong Zhao +11 more
TL;DR: In this paper, the following formula (I) and methods of their use and preparation are disclosed: and methods for their extraction and use and their preparation are described: [1]
Journal ArticleDOI
Development of SNAr Nucleophilic Fluorination: A Fruitful Academia-Industry Collaboration.
TL;DR: This Account summarizes the development of several strategies for generating high concentration solutions of anhydrous tetraalkylammonium fluoride in situ by designing reactions that involve an alternative concerted delivery of the fluoride to the ipso C(sp2) center, and develops a deoxyfluorination of arylfluorosulfonates using anHydrous Me4NF.
Journal ArticleDOI
Development and Application of O-(Trimethylsilyl)aryl Fluorosulfates for the Synthesis of Arynes.
TL;DR: A class of o-(trimethylsilyl)aryl fluorosulfates was synthesized by a concise method and successfully used as aryne precursors for the first time.
Journal ArticleDOI
A Broad-Spectrum Catalytic Amidation of Sulfonyl Fluorides and Fluorosulfates*.
TL;DR: In this article, a broad spectrum, catalytic method was developed for the synthesis of sulfonamides and sulfamates, which is particularly efficient for sterically hindered substrates.
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.
Journal ArticleDOI
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.