Sydnonimines as exogenous NO donors

Khmel'nitskaya, E. Yu.; Levina, V. I.; Трухачева, Л. А.; Grigoriev, N. B.; Калинин, В. Н.; Cherepanov, I. A.; Lebedev, S. N.; Граник, В. Г.

doi:10.1007/s11172-005-0199-2

Cited by 18 publications

(10 citation statements)

References 16 publications

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“…The existence of those atoms is characteristic of ylides and conjugated mesomeric betaines. Calculations show that the betaine 79a is ∆G = -9.3 kJ/mol more stable than the tautomeric carbene which is not visible in DMSO-d 6 solutions by NMR spectroscopy. The carbenes, however, were trapped as thiones in high yields.…”

Section: Interconversions Of Normal N-heterocyclic Carbenes (Nnhc) Anmentioning

confidence: 93%

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Recent advances in neutral and anionic N-heterocyclic carbene – betaine interconversions. Synthesis, characterization, and applications

Schmidt¹,

Wiechmann²,

Freese³

2013

Arkivoc

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Some mesoionic compounds, i.e. five-membered representatives of the class of conjugated mesomeric betaines (CMB), are in equilibrium with their tautomeric normal N-heterocyclic carbenes (nNHC). In addition, anionic N-heterocyclic carbenes, generated by deprotonation of mesoionic compounds, have been described. The first examples of conversions of crossconjugated mesomeric betaines (CCMB), 6-oxopyrimidinium-4-olates, into normal Nheterocyclic carbenes have been reported as well. CCMB such as imidazolium-4-carboxylate and pyrazolium-4-carboxylate can decarboxylate to form abnormal (aNHC) or remote N-heterocyclic carbenes (rNHC). Most conversions of betaines into N-heterocyclic carbenes start from pseudocross-conjugated mesomeric betaines (PCCMB) which can be regarded as heterocumulene adducts of nNHC. Thus, decarboxylations of imidazolium-2-carboxylates, 1,2,4-triazole-3-carboxylates, pyrazolium-3-carboxylates or indazolium-3-carboxylates yield N-heterocyclic carbenes which have been used in catalysis, complex chemistry, heterocyclic synthesis, and organocatalysis.

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Section: Interconversions Of Normal N-heterocyclic Carbenes (Nnhc) Anmentioning

confidence: 93%

“…In parallel, mesoionic compounds aroused much interest as biologically active compounds [5][6][7][8] and 1,3-dipoles in [2+3]-cycloadditions. 9,10 In 1955, Katritzky pointed out inconsistencies to be found in the literature and examined critically the value of the descriptive term "mesoionic".…”

Section: Scheme 1 the First Mesoionic Compound (1882)mentioning

confidence: 99%

Recent advances in neutral and anionic N-heterocyclic carbene – betaine interconversions. Synthesis, characterization, and applications

Schmidt¹,

Wiechmann²,

Freese³

2013

Arkivoc

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“…ImSyds were rst synthesized by two groups in parallel in 1957 8,9 and quickly received much attention because of their rich biological properties, 10 in particular in the cardiovascular eld. 11 As exogeneous NO donating agents they can modulate several functions of the cellular metabolism [12][13][14] and besides their main therapeutic indications as antithrombotic, antihypertensive and antianginal drugs, 15 ImSyds have more recently been investigated as selective dopamine reuptake inhibitors, 16,17 antimicrobial 18 and antifungal 19 compounds and plant growth stimulants. 20 ImSyd prodrugs have also been designed for the treatment of glaucomatous optic neuropathy and showed promising properties for a potential topical ocular formulation.…”

Section: Iminosydnones and Derivatives As Active Pharmaceutical Ingre...mentioning

confidence: 99%

A mechanochemical approach to the synthesis of sydnones and derivatives

et al. 2023

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“…Iminosydnones have been known for decades to display interesting biological activities, mostly through their capability to act as effective exogenous donors of nitric oxide. − Some derivatives are also used as medicines (Molsidomine, Sydnophen, and Mesocarb). In view of these remarkable biological applications, it is surprising that some members of the iminosydnone family have remained unexplored to date.…”

Section: Introductionmentioning

confidence: 99%

Fast and Bioorthogonal Release of Isocyanates in Living Cells from Iminosydnones and Cycloalkynes

et al. 2023

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Bioorthogonal click-and-release reactions are powerful tools for chemical biology, allowing, for example, the selective release of drugs in biological media, including inside animals. Here, we developed two new families of iminosydnone mesoionic reactants that allow a bioorthogonal release of electrophilic species under physiological conditions. Their synthesis and reactivities as dipoles in cycloaddition reactions with strained alkynes have been studied in detail. Whereas the impact of the pH on the reaction kinetics was demonstrated experimentally, theoretical calculations suggest that the newly designed dipoles display reduced resonance stabilization energies compared to previously described iminosydnones, explaining their higher reactivity. These mesoionic compounds react smoothly with cycloalkynes under physiological, copper-free reaction conditions to form a click pyrazole product together with a released alkyl-or aryl-isocyanate. With rate constants up to 1000 M −1 s −1 , this clickand-release reaction is among the fastest described to date and represents the first bioorthogonal process allowing the release of isocyanate electrophiles inside living cells, offering interesting perspectives in chemical biology.

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Sydnonimines as exogenous NO donors

Cited by 18 publications

References 16 publications

Recent advances in neutral and anionic N-heterocyclic carbene – betaine interconversions. Synthesis, characterization, and applications

Recent advances in neutral and anionic N-heterocyclic carbene – betaine interconversions. Synthesis, characterization, and applications

A mechanochemical approach to the synthesis of sydnones and derivatives

Fast and Bioorthogonal Release of Isocyanates in Living Cells from Iminosydnones and Cycloalkynes

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