- Molecular design principles of ionic liquids with a sulfonyl fluoride moiety
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The continued success of ionic liquids in applications ranging from energy to medicine poses the challenge to rapidly find new functional ionic liquids with desirable properties while developing practical, scalable syntheses. As a SuFExable functionality, the sulfonyl fluoride has become widely adopted throughout the field of chemical biology due, in part, to its unique stability-reactivity pattern, highlighting the underappreciated potential of the SVI-F motif in materials chemistry. For the first time, we herein report the development of a set of sulfonyl fluoride-functionalized ionic liquids with considerable structural diversityviaan efficient, modular, and orthogonal fluorosulfonylethylation procedure. The resulting SO2F-functionalized ionic milieu has properties consistent with its classification as ionic liquids. We employed a combination of molecular design, synthesis, computational modeling, and X-ray crystallographic studies to gain in-depth understanding of their structure-property correlations. The diversification of the SO2F-bearing salts is extended to include active pharmaceutical precursors, allowing for access to functional materials witha priorilow toxicity.
- Siegel, David J.,Anderson, Grace I.,Cyr, Noah,Lambrecht, Daniel S.,Zeller, Matthias,Hillesheim, Patrick C.,Mirjafari, Arsalan
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- 2-Azidoethane-1-sulfonylfluoride (ASF): A Versatile Bis-clickable Reagent for SuFEx and CuAAC Click Reactions
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A new reagent, 2-azidoethane-1-sulfonylfluoride (ASF), was synthesized from 2-chloroethane-1-sulfonyl fluoride in 50g-scale with 87 % yield. This novel reagent possesses two selectively clickable functionalities to be used for both CuAAC and SuFEx click reactions. The application of this reagent ASF to the construction of a class of novel 1,2,3-triazole derived S(VI)-F analogs was achieved in a quick, efficient and atom-economical manner. Orthogonally clickable construction of a new class of dendrimers was also accomplished.
- Zhang, Xu,Moku, Balakrishna,Leng, Jing,Rakesh,Qin, Hua-Li
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- Metal-Free Synthesis of Functional 1-Substituted-1,2,3-Triazoles from Ethenesulfonyl Fluoride and Organic Azides
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The boom in growth of 1,4-disubstituted triazole products, in particular, since the early 2000’s, can be largely attributed to the birth of click chemistry and the discovery of the CuI-catalyzed azide–alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1-substituted-1,2,3-triazoles has been surprisingly more challenging. Reported here is 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). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal-free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1-substituted-1,2,3-triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1-substituted triazolium sulfonyl fluoride salts.
- Giel, Marie-Claire,Smedley, Christopher J.,Mackie, Emily R. R.,Guo, Taijie,Dong, Jiajia,Soares da Costa, Tatiana P.,Moses, John E.
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supporting information
p. 1181 - 1186
(2019/12/11)
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- Sulfur(VI) fluoride compounds and methods for the preparation thereof
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This application describes a compound represented by Formula (I): (I) wherein: Y is a biologically active organic core group comprising one or more of an aryl group, a heteroaryl aryl group, a nonaromatic hydrocarbyl group, and a nonaromatic heterocyclic group, to which Z is covalently bonded; n is 1, 2, 3, 4 or 5; m is 1 or 2; Z is O, NR, or N; X1 is a covalent bond or —CH2CH2—, X2 is O or NR; and R comprises H or a substituted or unsubstituted group selected from an aryl group, a heteroaryl aryl group, a nonaromatic hydrocarbyl group, and a nonaromatic heterocyclic group. Methods of preparing the compounds, methods of using the compounds, and pharmaceutical compositions comprising the compounds are described as well.
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Page/Page column 19; 36; 37; 51
(2018/11/23)
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- Ethenesulfonyl Fluoride (ESF): An On-Water Procedure for the Kilogram-Scale Preparation
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A two-step, on-water procedure for the synthesis of ethenesulfonyl fluoride (ESF) is described. 2-Chloroethanesulfonyl fluoride is made via a neat reaction with an aqueous, nearly saturated potassium bifluoride solution from readily available 2-chloroetha
- Zheng, Qinheng,Dong, Jiajia,Sharpless, K. Barry
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p. 11360 - 11362
(2016/11/29)
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- Hydrocarbylethyl sulfonyl fluoride
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Hydrocarbylethyl sulfonyl fluorides in which the hydrocarbyl substituent contains at least 3 carbon atoms, can be prepared by reacting 2-mercaptoethanol with chlorine to form chloroethyl sulfonyl chloride which is treated with aqueous potassium fluoride to yield chloroethyl sulfonyl fluoride, followed by treatment with magnesium oxide to yield vinyl sulfonyl fluoride. The vinyl sulfonyl fluoride is adducted to a hydrocarbyl substituent precursor, such as an olefin or halogenated olefin. A representative compound is polyisobutenyl sulfonyl fluoride. The hydrocarbylethyl sulfonamide products for which the hydrocarbylethyl sulfonyl fluorides are intermediates are useful as additives for lubricating oils.
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