N-Perfluoroalkylsulfonylimido derivatives of arenecarboxylic acid amides and their oxidative aza Hofmann rearrangement

Yagupol’skii, L. M.; Maletina, I. I.; Sokolenko, Liubov V.; Vlasenko, Yurii; Buth, S.A.

doi:10.1016/j.jfluchem.2008.03.001

Cited by 11 publications

(10 citation statements)

References 13 publications

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“…To achieve full conversion in these challenging cases simply switching to a one-pot approach was tested. Gratifyingly, when nucleophile was added after just 10 minutes reaction of amidine with oxidant at 30°C, full conversion and significantly improved isolated yields were obtained (up to 35%) (entries 11,13,15,17,19,22). For piperazines the yield can be further increased to over 90% when three equivalents were added (entries 20 and 23).…”

Section: Resultsmentioning

confidence: 99%

“…In accordance with the observations of Yagupolskii a tosyl gave a high yield of the corresponding guanidine (entry 7). [11] Next, different substituents in the phenyl ring of N-benzylbenzamidine were tested (Table 2). Both electron donating (entries 8-11) and withdrawing (entries 12-16) substituents are well tolerated.…”

Section: Resultsmentioning

confidence: 99%

“…Aza Hofmann rearrangement of N-alkanesulfonyl-arenamidines with diacetoxyiodotoluene into Nalkanesulfonyl-N'-arylcarbodiimide in glyme has been described by Yagupolskii. [11,12] Similar to the Tiemann rearrangement, the arenamidine requires a very strong electron withdrawing sulfonyl group as activator for rearrangement and only reactions with morpholine (one-pot) were reported. Moreover, in general only low yields of N-aryl-N'-(alkylsulfonyl)morpholine-4-carboximidamides were obtained and no straightforward and sufficiently mild procedure for removal of the strong electron withdrawing Nactivating sulfonyl group was provided.…”

Section: Introductionmentioning

confidence: 99%

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Guanidine Synthesis: Use of Amidines as Guanylating Agents

Baeten

Maes

2016

Adv Synth Catal

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The use of amidines for the tandem or one pot synthesis of guanidines is reported. Guanidines are obtained by oxidative rearrangement of readily available and stable amidines into carbodiimides, followed by in situ reaction with amines. The protocol can be executed under mild reaction conditions (30°C), in a green solvent (dimethyl carbonate). The amine scope is broad, including sterically hindered, oxidation sensitive and chiral amines. Examples for the synthesis of both acyclic and cyclic guanidines are provided. 2-PrOPhI byproduct, generated from the oxidant 2-PrOPhINTs, can be isolated in high yields making regeneration of the hypervalent iodine reagent possible. The utility and greenness of the synthetic method is demonstrated by a new route towards the antihypertensive drug Pinacidil. The Process Mass Intensity (PMI) of the new route is only 24% of the classical one.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Guanidine Synthesis: Use of Amidines as Guanylating Agents

Baeten

Maes

2016

Adv Synth Catal

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“…The presence of several NH signals in the 1 H NMR spectrum may be related to equilibrium between intramolecularly H-bonded and free amino species. Finally, the lack of tautomeric form TfNHC(Ar)=NH was shown in [11] for TfN=C(Ar)NH 2 both in crystal and in solution.…”

Section: Rnhmentioning

confidence: 92%

Synthesis and structure of N-(diaminomethylidene)- and N-[bis(cyclohexylamino)methylidene]trifluoromethanesulfonamides

et al. 2011

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N-Trifluoromethylsulfonyl-substituted guanidines CF 3 SO 2 N=C(NHR) 2 (R = H, cyclohexyl) were synthesized in nearly quantitative yield by reactions of N-sulfinyltrifluoromethanesulfonamide CF 3 SO 2 N=S=O with urea and of trifluoromethanesulfonamide with N, N′-dicyclohexylcarbodiimide. N-[Bis(cyclohexylamino)methylidene]trifluoromethanesulfonamide was subjected to protonation with trifluoromethanesulfonic acid and bis(trifluoromethanesulfonyl)imide, and the structure of the resulting salts and initial N-trifluoromethylsulfonylguanidines was studied by NMR and IR spectroscopy and DFT quantum-chemical calculations.

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“…In a course of a systematic research on nucleophilic rearrangements of carbonyl compounds analogues in which the sp 2 -hybridized oxygen atom is replaced by a trifluoromethylsulfonylimino group, we previously reported that aza analogues of acid azides, arenehydroxamic acids and carboxamides undergo the aza Curtius [1], Lossen [2] and Hofmann [3] rearrangements. The aza Curtius reaction was shown to proceed under mild conditions yielding the carbodiimides containing the 5 5NSO 2 CF 3 group [1].…”

Section: Introductionmentioning

confidence: 99%