Trifluoromethanesulfonamides and Related Compounds

Shainyan, B. А.; Tolstikova, L. L.

doi:10.1021/cr300220h

Cited by 103 publications

(70 citation statements)

References 416 publications

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“…Analysis of the 1 H NMR spectra of the reaction mixture showed the presence of unreacted cis isomers 4 and 6 at the same ratio to trans isomers 5 and 7 as in the initial isomer mixture. Insofar as the difference in the electron-withdrawing powers of the 4-nitrobenzenesulfonyl and trifluoromethanesulfonyl groups is not large (σ I 0.61 and 0.71, respectively [26]), our results confirm the assumption that trifluoromethanesulfonamide exhibits a specific reactivity [27], which differs from the reactivity of even its closest analog, electron-deficient 4-nitrobenzenesulfonamide. 4 The IR spectra were recorded in KBr on Varian 3100 FT-IR and Bruker Vertex 70 spectrometers.…”

Section: Methodssupporting

confidence: 78%

Oxidative cycloaddition of electron-deficient arenesulfonamides to hexa-1,5-diene

et al. 2015

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The reaction of electron-deficient arenesulfonamides 4-XC 6 H 4 SO 2 NH 2 (X = Cl, NO 2 ) with hexa-1,5-diene in the oxidative system t-BuOCl-NaI afforded cis-and trans-isomeric 1-(arenesulfonyl)-2,5-bis-(iodomethyl)pyrrolidines. The diastereoisomers were separated, and their structure was determined by NMR spectroscopy and X-ray analysis. No further cyclization of these compounds into 3,8-diazabicyclo[3.2.1]octanes was observed. n = 1, 2; EWG = COOEt, COMe, COPh, CN.

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Section: Methodssupporting

confidence: 78%

Oxidative cycloaddition of electron-deficient arenesulfonamides to hexa-1,5-diene

et al. 2015

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“…[50] 2013 Trifluoromethanesulfonamides and Related Compounds. [54] 2014 Electrolytesand Interphases in Li-Ion Batteriesand Beyond. [55] Brønsted acid (HNTf 2 )p ossesses superacid properties, thereby giving rise to as table anion.…”

Section: [N(so 2 R F ) 2 ] à Anions-trifluoromethanesulfonamides/ Trimentioning

confidence: 99%

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

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This Review gives a comprehensive overview of the most topical weakly coordinating anions (WCAs) and contains information on WCA design, stability, and applications. As an update to the 2004 review, developments in common classes of WCA are included. Methods for the incorporation of WCAs into a given system are discussed and advice given on how to best choose a method for the introduction of a particular WCA. A series of starting materials for a large number of WCA precursors and references are tabulated as a useful resource when looking for procedures to prepare WCAs. Furthermore, a collection of scales that allow the performance of a WCA, or its underlying Lewis acid, to be judged is collated with some advice on how to use them. The examples chosen to illustrate WCA developments are taken from a broad selection of topics where WCAs play a role. In addition a section focusing on transition metal and catalysis applications as well as supporting electrolytes is also included.

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“…Based on its low pK a of 1.6, 13 initial work explored derivatives of saccharine. 18 Metal salts and ionic liquids derived from TFSI have attracted a great deal of attention from scientists researching transport materials for lithium ion batteries. ditosylamines) could undergo substitution and elimination.…”

Section: Introductionmentioning

confidence: 99%

“…14 Unfortunately these were found to undergo preferential attack at the carbonyl carbon; however, the authors discovered that bis(sulfonyl)imides (e.g. 18,19 Despite this trend, the activation of nitrogen as a nucleofuge remains a rare strategy. 14 The most common activation in this vein appears to be through the addition of dual triflyl groups to form bis(trifluoromethanesulfonyl)imide derivatives.…”

Section: Introductionmentioning

confidence: 99%

Nucleofugality in oxygen and nitrogen derived pseudohalides in Menshutkin reactions: the importance of the intrinsic barrier

Spahlinger

Jackson

2014

Phys. Chem. Chem. Phys.

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In order to study the nucleofugality of polyatomic anionic leaving groups derived from oxygen and nitrogen, a contingent of 19 methylating agents consisting of amines or alcohols activated with carbonyl or sulfonyl substituents has been examined via ab initio calculations. We have calculated gas phase activation energies for alkylation of ammonia, and methyl cation affinities. We find that polyatomic anionic leaving groups derived from nitrogen will have higher activation energies for Menshutkin (SN2) alkylation even when they have similar methyl cation affinities. This inherent deficit in the nucleofugality of nitrogen-derived leaving groups appears to be a result of the way bond cleavage is synchronized with bond formation to the incoming ammonia nucleophile. The nitrogen leaving groups showed greater dissociation from the methyl fragment than oxygen leaving groups relative to the length of the forming carbon-nitrogen bond. Additionally the second sulfonyl group present in a sulfonimide appears to be less effective at activating nitrogen due to a preference for tetrahedral geometries at the departing nitrogen in the transition states involving leaving sulfonamide groups. Optimal delocalization of electron density is therefore frustrated due to the geometry of the leaving group.

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Trifluoromethanesulfonamides and Related Compounds

Cited by 103 publications

References 416 publications

Oxidative cycloaddition of electron-deficient arenesulfonamides to hexa-1,5-diene

Oxidative cycloaddition of electron-deficient arenesulfonamides to hexa-1,5-diene

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Nucleofugality in oxygen and nitrogen derived pseudohalides in Menshutkin reactions: the importance of the intrinsic barrier

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