Assembling of 3,6-diazabicyclo[3.1.0]hexane framework in oxidative triflamidation of substituted buta-1,3-dienes

Moskalik, M. Yu.; Astakhova, Vera V.; Schilde, Uwe; Sterkhova, Irina V.; Shainyan, B. А.

doi:10.1016/j.tet.2014.09.050

Cited by 21 publications

(9 citation statements)

References 44 publications

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“…Both linear and cyclic dienes have been investigated as substrates in oxidative sulfamidation, with special attention having been paid to sometimes drastic differences in reactivity of triflamide and nonfluorinated arenesulfonamides. Thus, whereas arenesulfonamides react with 2,3‐dimethylbuta‐2,3‐diene ( 92 ) to give linear unsaturated products 93 through oxidative 1,4‐addition of two sulfonamide residues, triflamide reacts with 92 and with 2,5‐dimethylhexa‐2,4‐diene ( 94 ) through 1,4‐cyclization followed by 1,2‐addition to the intermediate pyrrolines 95 and 96 to afford bicyclic products 97 and 98 , respectively (Scheme ) . The structures of 3,6‐diazabicyclo[3.1.0]hexanes 97 and 98 were established by X‐ray analysis.…”

Section: Unsaturated Triflamides Via Oxidative Triflamidation Of Dmentioning

confidence: 99%

“…Note that the reactions with triflamide were carried out at low temperature; when the reaction with diene 94 was performed at room temperature, only the cyclic product of iodooxidation of 2,5‐dimethylhexa‐2,4‐diene – 4‐iodo‐2,2,5,5‐tetramethyltetrahydrofuran‐3‐ol – was formed …”

Section: Unsaturated Triflamides Via Oxidative Triflamidation Of Dmentioning

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 Via Oxidative Triflamidation Of Dmentioning

confidence: 99%

Section: Unsaturated Triflamides Via Oxidative Triflamidation Of Dmentioning

confidence: 99%

Unsaturated Derivatives of Trifluoromethanesulfonamide

Shainyan

2018

Eur J Org Chem

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“…The scale of applicability of Bu t OI-mediated amidation is not limited by the preparation of aziridines, since the formation of other valuable heterocycles was also reported [ 3 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 ]. Thus, non-activated alkenes when treated with benzamides in presence of Bu t OI afford oxazolines [ 55 ].…”

Section: Introductionmentioning

confidence: 99%

Trifluoromethanesulfonamide vs. Non-Fluorinated Sulfonamides in Oxidative Sulfamidation of the C=C Bond: An In Silico Study

2020

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A theoretical analysis of the reaction of oxidative sulfamidation of several alkenes was performed in order to explain the various experimental observations and different reactivity of triflamide and non-fluorinated sulfonamides. Transformations occurring in the system alkene–sulfonamide in the presence of oxidative system (ButOCl + NaI) were analyzed at the MP2/DGDZVP//B3LYP/DGDZVP level of theory using the IEF-PCM method for taking into account the solvent acetonitrile (MeCN) effect. As the model substrates, styrene, trimethyl(vinyl)silane, dimethyl(divinyl)silane and diphenyl(divinyl)silane were chosen and mesylamide, triflamide, tosylamide and p-nosylamide were taken as the reagents. ButOI generated from ButOCl and NaI reacts with sulfonamides to give N-iodinated sulfonamides RSO2NHI and RSO2NI2 as active intermediates, the iodinating activity of the latter being notably higher. The analysis allowed to answer such challenging questions as different reactivity of nonfluorinated sulfonamides leading to aziridination and of triflamide resulting in the formation the main products of bis-triflamidation, or different regioselectivity of halogenation of styrene and trimethyl(vinyl)silane caused by a linear intermediate iodonium cation in the former case and a cyclic one in the latter.

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“…The reactions of oxidative triflamidation of dienes in the oxidative system ( t ‐BuOCl+NaI) proceed in different manner, leading to the products of 1,2‐ or 1,4‐addition with heterocyclization . With 1,4‐ or 2,3‐dimethylated butadienes‐1,3, the properly methylated 3,6‐bis(triflyl)diazabicyclo[3.1.0]hexanes were formed via two successive heterocyclizations …”

Section: Introductionmentioning

confidence: 99%

“…Apart from the above cited heterocyclization of dimethylated butadienes‐1,3 leading to the products containing the N ‐triflyl motif in the molecule, several routes to pyrrolidines having the amide or sulfonamide motif in the 3‐position of the ring are known. One of them is the oxirane ring opening in the corresponding epoxy‐derivatives followed, as a rule, by acylation with acyl halides to give 3‐acylated pyrrolidines .…”

Section: Introductionmentioning

confidence: 99%

1,4-Diphenyl-1,3-butadiene and 1,1,4,4-Tetraphenyl-1,3-butadiene in the Reactions of Oxidative Sulfamidation and Trifluoroacetamidation

et al. 2017

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Sulfonamides react with 1,4-diphenyl-1,3-butadiene in oxidative conditions to give the products of heterocyclization, substituted N-sulfonylpyrrolidines. In contrast, 1,1,4,4-tetraphenyl-1,3butadiene with triflamide in the same conditions unexpectedly gives only 3,4,5,5-tetraphenyldihydrofuran-2(3H)-one as a result of oxidation/heterocyclization with migration of several phenyl groups. Oxidative trifluoroacetamidation of 1,4-diphenyl-1,3butadiene leads to a similar product of heterocyclization, N-(trifluoroacetyl)pyrrolidine, but also to the product of oxyamidation at only one double bond and, unexpectedly, the product of splitting of the C=C bond, N,N'-(phenylmethanediyl) bis(trifluoroacetamide), in a high total yield. Tentative mechanisms of the reactions are proposed.

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Assembling of 3,6-diazabicyclo[3.1.0]hexane framework in oxidative triflamidation of substituted buta-1,3-dienes

Cited by 21 publications

References 44 publications

Unsaturated Derivatives of Trifluoromethanesulfonamide

Unsaturated Derivatives of Trifluoromethanesulfonamide

Trifluoromethanesulfonamide vs. Non-Fluorinated Sulfonamides in Oxidative Sulfamidation of the C=C Bond: An In Silico Study

1,4-Diphenyl-1,3-butadiene and 1,1,4,4-Tetraphenyl-1,3-butadiene in the Reactions of Oxidative Sulfamidation and Trifluoroacetamidation

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