Oxidative addition/cycloaddition of arenesulfonamides and triflamide to N-allyltriflamide and N,N-diallyltriflamide

Shainyan, B. А.; Astakhova, Vera V.; Ganin, Anton S.; Moskalik, M. Yu.; Sterkhova, Irina V.

doi:10.1039/c7ra05831d

Cited by 17 publications

(5 citation statements)

References 30 publications

(7 reference statements)

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“…The marked Brønsted acidity of the “NHTf” motif (pKa ca. 6.3, for TfNH 2 ), [3a–c] the ready access to unprotected amino groups [3d–f] and the chemical flexibility of the allyl unit [2a,c] account for the prominent role played by this class of nitrogen‐based compounds in the organic chemistry scenario.…”

Section: Figurementioning

confidence: 99%

Visible‐Light‐Assisted Synthesis of Allylic Triflamides via Dual Acridinium/Co Catalysis

et al. 2021

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A dehydrogenative functionalization of styryl carbon‐carbon double bonds with triflamide is described via dual visible‐light photoredox/cobaloxime catalysis. A range of allylic triflamides (20 examples) were isolated in moderate to good yields (up to 88%) under stoichiometric acceptorless conditions. Dedicated labelling, as well as spectroscopic experiments, enabled to shed light on the concatenated photo‐ and chemo‐catalytic cycles.

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Section: Figurementioning

confidence: 99%

Visible‐Light‐Assisted Synthesis of Allylic Triflamides via Dual Acridinium/Co Catalysis

et al. 2021

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“…Whereas the reaction between N ‐allyltriflamide and triflamide leads to N , N′ , N′′ ‐propane‐1,2,3‐triyltris(triflamide) ( 21 ) in quantitative yield, 2,5‐bis(chloromethyl)‐1,4‐bis[(trifluoromethyl)sulfonyl]piperazine ( 22 ) was the only product isolated from reactions between 8 and either arenesulfonamides or trifluoroacetamide, which acted only as chlorine carriers (Scheme ). From X‐ray analysis, the two CH 2 Cl groups in 22 are trans to each other …”

Section: Unsaturated Triflamides Through Amination Of Triflic Anhymentioning

confidence: 99%

“…With a twofold excess of triflamide at –30 °C, in addition to 23 – 25 , diadduct 26 is formed (Scheme ). The structures of heterocycles 24 and 25 were established by X‐ray analysis …”

Section: Unsaturated Triflamides Through Amination Of Triflic Anhymentioning

confidence: 99%

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Unsaturated Derivatives of Trifluoromethanesulfonamide

Shainyan

2018

Eur J Org Chem

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Unsaturated derivatives of trifluoromethanesulfonamide (CF3SO2NH2, triflamide, TfNH2) of general formula TfNRR′ where R and/or R′ contain C=C or C≡C bonds, are of particular interest in triflate chemistry because they open the way for further functionalization and provide access to new adducts and cycloadducts. Two approaches to these compounds have been developed in our group. One is treatment of triflic anhydride (or fluoride) with unsaturated amines, or alkylation of triflamide with unsaturated alkyl halides. The second approach consists of oxidative triflamidation of dienes, with one C=C bond remaining intact. Another class of unsaturated triflamide derivatives is that of N‐alkylidenetriflamides (TfN=R). At the time our comprehensive review on triflamides and related compounds covering the literature up to 2012 was published, very little information on unsaturated triflamides was available. Since then, research in this area has expanded. In this review we demonstrate new examples of unusual reactivity of unsaturated triflamides, such as unprecedented splitting of α,ω‐bis(triflamidomethyl)diacetylene, diverse courses of oxidative triflamidation and arenesulfonamidation of dienes, different routes of cycloaddition of fluorinated and non‐fluorinated N‐sulfinylsulfonamides to carbodiimides, isomerization, etc. The high NH‐acidity, the strong electron‐acceptor ability and good nucleofugality of the triflyl and triflamido groups, and the presence of multiple bonds in the unsaturated triflamides all make them both interesting objects for investigations of hydrogen bonding and self‐organization processes, as well as valuable synthons in organic chemistry.

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“…Earlier, we studied a lot of unsaturated substrates in the reactions of oxidative sulfonamidation as summarized in review [ 12 ] but only a few of them contained electron-withdrawing groups. Among them were divinyl sulfone and divinyl sulfoxide, which reacted with triflamide in the system t -BuOCl/NaI via iodotriflamidation with subsequent cyclization into 2,6-diiodo-4-(triflyl)thiomorpholine 1,1-dioxide [ 13 ], mono- and diallyltriflamides, which under the same conditions reacted with carboxamides and sulfonamides via halogenation of the double bond [ 14 , 15 ] and/or iodosulfonamidation and cyclization to 3,7-diiodo-1,5-bis(triflyl)-1,5-diazocane and 3,7,9-tris(triflyl)-3,7,9- triazabicyclo[3.3.1]nonane [ 15 ], and mono- and diallyl ethers and allyl acetate, which on cooling to −30 °C gave the products of triflamidation or cyclization [ 16 ].…”

Section: Introductionmentioning

confidence: 99%

Triflamidation of Allyl-Containing Substances:Unusual Dehydrobromination vs. Intramolecular Heterocyclization

et al. 2022

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Allyl halides with triflamide under oxidative conditions form halogen-substituted amidines. Allyl cyanide reacts with triflamide in acetonitrile or THF solutions in the presence of NBS to give the products of bromotriflamidation with a solvent interception, whereas in CH2Cl2 two regioisomers of the bromotriflamidation product without a solvent interception were obtained. The formed products undergo base-induced dehydrobromination to give linear isomers with the new C=C bond conjugated either with the nitrile group or the amidine moiety or alkoxy group. Under the same conditions, the reaction of allyl alcohol with triflamide gives rise to amidine, which was prepared earlier by the reaction of diallyl formal with triflamide. Unlike their iodo-substituted analogs, bromo-substituted amidines successfully transform into imidazolidines under the action of potassium carbonate.

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Oxidative addition/cycloaddition of arenesulfonamides and triflamide to N-allyltriflamide and N,N-diallyltriflamide

Abstract: Mono- and diallyltriflamides react with triflamide in the oxidative system t-BuOCl + NaI to give the products of addition and cycloaddition, unlike the reaction of N-allyltriflamide with arenesulfonamides or trifluoroacetamide leading to chlorination and cyclodimerization.

Cited by 17 publications

References 30 publications

Visible‐Light‐Assisted Synthesis of Allylic Triflamides via Dual Acridinium/Co Catalysis

Visible‐Light‐Assisted Synthesis of Allylic Triflamides via Dual Acridinium/Co Catalysis

Unsaturated Derivatives of Trifluoromethanesulfonamide

Triflamidation of Allyl-Containing Substances:Unusual Dehydrobromination vs. Intramolecular Heterocyclization

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