Oxidative addition of trifluoromethanesulfonamide to cycloalkadienes

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

doi:10.1016/j.tet.2012.10.099

Cited by 27 publications

(20 citation statements)

References 28 publications

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“…No unsaturated triflamide derivatives were obtained with linear dienes in Scheme , but reactions with cyclic dienes in some cases successfully led to triflamides containing the N ‐allyl motif in the molecule. Thus, oxidative triflamidation of the conjugated cyclodienes (cyclopentadiene and cyclohexa‐1,3‐diene) proceeds as trans ‐iodotriflamidation or bistriflamidation, as confirmed by X‐ray analysis of compounds 105 and 106 (Scheme ) …”

Section: Unsaturated Triflamides Via Oxidative Triflamidation Of Dmentioning

confidence: 99%

“…Although there are precedents for C=C bond lengths in the 1.24–1.29 Å range, the double bond in molecule 106 seems to be the shortest one. [59b]…”

Section: Unsaturated Triflamides Via Oxidative Triflamidation Of Dmentioning

confidence: 99%

“…Nonconjugated cyclodienes react differently from their conjugated isomers. Cyclohexa‐1,4‐diene ( 108 ), for example, gives an unsymmetrically substituted product (as judged from the presence of six signals for the ring carbon atoms in its 13 C NMR spectrum) of general formula C 8 H 10 ClF 6 IN 2 O 4 S 2 , which could have had the structure of N , N′ ‐(2‐chloro‐5‐iodocyclohexane‐1,4‐diyl)bis(triflamide) ( 109a ) or of its positional isomers 109b or 109c …”

Section: Unsaturated Triflamides Via Oxidative Triflamidation Of Dmentioning

confidence: 99%

“…An attempt to replace the chlorine atom in 109 by iodine in order to facilitate the assignment unexpectedly gave trans‐N , N′ ‐cyclohex‐4‐en‐1,2‐diylbis(triflamide) ( 110 ), the structure of which was determined by X‐ray analysis (Figure ) …”

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%

“…Although there are precedents for C=C bond lengths in the 1.24–1.29 Å range, the double bond in molecule 106 seems to be the shortest one. [59b]…”

Section: Unsaturated Triflamides Via Oxidative Triflamidation Of Dmentioning

confidence: 99%

Section: Unsaturated Triflamides Via Oxidative Triflamidation Of Dmentioning

confidence: 99%

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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“…[2] Our recent paper was devoted to oxidative addition of trifluoromethanesulfonamide to 1,3-cyclodienes (cyclopentadiene and 1,3-cyclohexadiene) with the formation of the products of 1,2-addition. [3] The copper hexafluoroacetylacetonate catalyzed ring expansion of two dozens of vinyl aziridines to 3-pyrrolines proceeding as [1,3]-sigmatropic rearrangement in up to quantitative yield was meticulously studied. [4] Even these scarce literature data show that 1,3-dienes with sulfonylnitrenes (or their predecessors) can give the products of 1,2-or 1,4-addition, the latter sometimes being the products of further transformation of the former.…”

Section: Introductionmentioning

confidence: 99%

Computational study of singlet and triplet sulfonylnitrenes insertion into 1,3‐butadienes: 1,2‐ or 1,4‐cycloaddition?

Shainyan

Kuzmin

2014

J of Physical Organic Chem

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The formation of N-trifluoromethylsulfonyl-2-vinylaziridine and N-trifluoromethylsulfonyl-3-pyrroline by the reaction of the singlet and triplet trifluoromethanesulfonylnitrenes with s-cisand s-trans-1,3-butadienes was studied theoretically at the B3LYP/6-311++G(d,p) and M06-2X/6-311++G(d,p) levels of theory. The singlet trifluoromethanesulfonylnitrene adds to s-cisand s-trans-1,3-butadiene exothermally in one step to give the product of 1,2-cycloaddition, N-trifluoromethylsulfonyl-2vinylaziridine, the energy decreasing by 88.5 and 86.2 kcal/mol at the B3LYP level and by 105.2 and 103.0 kcal/mol at the M06-2X level, respectively. The formed 2-vinylaziridine can undergo rotation about the C(2)-C sp2 bond with the barrier not exceeding 3.5 kcal/mol and to rearrange into N-trifluoromethylsulfonyl-3-pyrroline. The triplet trifluoromethanesulfonylnitrene reacts with s-cisand s-trans-1,3-butadiene in two steps. The first exothermic step is the formation of the triplet diradical adducts. The second step is the spin inversion with the energy raising by 5.8 and 17.8 kcal/mol at the B3LYP level and by 11.0 and 20.8 kcal/mol at the M06-2X level for the adducts to s-cisand s-trans-1,3-butadiene, respectively. Recombination of the radical centers occurs selectively to give N-trifluoromethylsulfonyl-2-vinylaziridine that is exothermally rearranged into N-trifluoromethylsulfonyl-3-pyrroline with the energy barrier of 40 kcal/mol at the B3LYP level and of 50 kcal/mol at the M06-2X level.

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Addition Reactions: Polar Addition

Kočovský¹

2016

Organic Reaction Mechanisms · 2013

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Oxidative addition of trifluoromethanesulfonamide to cycloalkadienes

Cited by 27 publications

References 28 publications

Unsaturated Derivatives of Trifluoromethanesulfonamide

Unsaturated Derivatives of Trifluoromethanesulfonamide

Computational study of singlet and triplet sulfonylnitrenes insertion into 1,3‐butadienes: 1,2‐ or 1,4‐cycloaddition?

Addition Reactions: Polar Addition

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