Bromination of highly unsaturated trifluoromethanesulfonamide derivatives

Shainyan, B. А.; Ushakova, I. V.; Danilevich, Yu. S.

doi:10.1134/s1070428015070064

Cited by 5 publications

(3 citation statements)

References 10 publications

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“…N ‐Propargyltriflamide ( 27) is brominated to give a mixture of the cis and trans isomers of N ‐(2,3‐dibromoallyl)triflamide (TfNHCH 2 CBr=CHBr, 43 ) in the ratio ( Z )‐ 43 /( E )‐ 43 = 24:76 . Apparently, bromination can proceed both via the open bromovinyl cation and via the bromirenium ion to afford both the cis and trans isomers .…”

Section: Unsaturated Triflamides Through Amination Of Triflic Anhymentioning

confidence: 99%

“…After addition of the second equivalent of bromine to this mixture the starting amide 32 and monoadduct 44 disappear and a mixture of 45 / 46 = 70:30 can be isolated and separated by column chromatography. Isomer ( Z , Z )‐ 45 was also identified as a minor product in a small proportion in the mixture with ( E , E )‐ 45 (Scheme ) …”

Section: Unsaturated Triflamides Through Amination Of Triflic Anhymentioning

confidence: 99%

“…Compound 47 did not give single crystals suitable for X‐ray, but DFT calculations, starting with the planar structure, gave a practically orthogonal structure of the molecule with a C=C–C=C dihedral angle of 90.8°, the orthogonalization leading to the energy gain of ca. 30 kcal mol –1 …”

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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Section: Unsaturated Triflamides Through Amination Of Triflic Anhymentioning

confidence: 99%

Section: Unsaturated Triflamides Through Amination Of Triflic Anhymentioning

confidence: 99%