- Water-Involved Ring-Opening of 4-Phenyl-1,2,4-triazoline-3,5-dione for “Photo-Clicked” Access to Carbamoyl Formazan Photoswitches In Situ
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Cyclic azodicarbonyl derivatives, particularly 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), commonly serve as arenophile, dienophile, enophile and electrophile. Perplexed by its instability in aqueous environment, there are few studies focused on the transient intermediate produced by hydrolysis of PTAD to achieve synthetic significance. Herein, we describe a “photo-click” method that involves nitrile imine (NI) from diarylsydnone to capture the diazenecarbonyl-phenyl-carbamic acid (DACPA) generated by water-promoted ring-opening of PTAD. DFT calculation reveal that H-bonding interactions between PTAD and water are vital to form DACPA which exhibited an umpolung effect during ligation by nature bond orbit (NBO) analysis. The ultra-fast ligation resulted in carbamoyl formazans, as a unique Z?E photo-switchable linker on target molecules, including peptide and drugs, with excellent anti-fatigue performance. This strategy is showcased to construct highly functionalized carbamoyl formazans in situ for photo-pharmacology and material studies, which also expands the chemistry of PTAD in aqueous media.
- Zheng, Yuanqin,Zhou, Yuqiao,Zhang, Yan,Deng, Pengchi,Zhao, Xiaohu,Jiang, Shichao,Du, Guangxi,Shen, Xin,Xie, Xinyu,Su, Zhishan,Yu, Zhipeng
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- Exploiting Synergistic Catalysis for an Ambient Temperature Photocycloaddition to Pyrazoles
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Sydnone-based cycloaddition reactions are a versatile platform for pyrazole synthesis, however they operate under harsh conditions (high temperature and long reaction times). Herein we report a strategy that addresses this limitation utilizing the synergistic combination of organocatalysis and visible-light photocatalysis. This new approach proceeds under ambient conditions and with excellent levels of regiocontrol. Mechanistic studies suggest that photoactivation of sydnones, rather than enamines, is key to the successful implementation of this process.
- Lakeland, Christopher P.,Watson, David W.,Harrity, Joseph P. A.
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supporting information
p. 155 - 159
(2019/12/11)
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- Mechanosynthesis of sydnone-containing coordination complexes
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N-Phenyl-4-(2-pyridinyl) sydnone was shown to act as a four-electron donor N,O-ligand in unprecedented coordination complexes featuring three different metallic centers (Co, Cu, and Zn). Starting with various anilines, the use of a ball-mill efficiently enabled the synthesis of N-arylglycines, subsequent nitrosylation and cyclization into sydnones, and further metalation.
- Pétry, Nicolas,Vanderbeeken, Thibaut,Malher, Astrid,Bringer, Yoan,Retailleau, Pascal,Bantreil, Xavier,Lamaty, Frédéric
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p. 9495 - 9498
(2019/08/15)
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- Anionic N-heterocyclic carbenes by decarboxylation of sydnone-4-carboxylates
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Unstable N-heterocyclic carbenes can be masked and stabilized as pseudo-cross-conjugated hetarenium-carboxylates which decarboxylate on warming. This study deals with the decarboxylation of carboxylates of mesoionic compounds to generate anionic N-heteroc
- Lücke, Ana-Luiza,Wiechmann, Sascha,Freese, Tyll,Nieger, Martin,F?ldes, Tamás,Pápai, Imre,Gjikaj, Mimoza,Adam, Arnold,Schmidt, Andreas
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p. 2092 - 2099
(2018/03/26)
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- Sydnone Reporters for Highly Fluorogenic Copper-Free Click Ligations
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Bioorthogonal fluorescent turn-on reactions are attractive for the sensitive real-time detection of a variety of phenomena including bioconjugation, chemical reactivity, and material assembly. Herein we describe the use of 3,4-disubstituted sydnones, a singular class of mesoionic dipoles, for highly fluorescent turn-on copper-free click cycloadditions with the fluorogenic dibenzocyclooctyne Fl-DIBO. Coherent with time-dependent density functional theory calculations, the pyrazole cycloadducts were found to be highly fluorescent with compelling photophysical properties including excellent fluorescence enhancement (up to 240-fold), high quantum yields (over 45%), and large Stokes shift (over 100 nm). Furthermore, the good stability and reactivity of 4-chlorosydnones with Fl-DIBO allowed us to employ them as chemical reporters for the challenging detection of modified-proteins in complex cellular extracts, with exquisite specificity in no-wash conditions. This novel fluorogenic system significantly expands our chemical biology toolbox and should be beneficial in countless applications.
- Favre, Camille,De Cremoux, Lucie,Badaut, Jerome,Friscourt, Frédéric
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p. 2058 - 2066
(2018/02/23)
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- Synthesis and crystal structure of 4-trifluoroacetyl-3-phenylsydnone
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4-Trifluoroacetyl-3-phenylsydnone was first synthesized by trifluoromethylation of 4-formyl-3-phenylsydnone followed by oxidation of the corresponding trifluoromethyl alcohol. The structure of the product was determined by single-crystal X-ray analysis.
- Kawase, Masami,Saijo, Ryosuke,Mori, Shigeki,Uno, Hidemitsu
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p. 2103 - 2110
(2017/11/21)
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- Novel sydnone derivatives carrying azidomethyl-1,2, 4-oxadiazole unit and their 1,3-dipolar cycloadditions
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A series of 1,2,4-oxadiazolymethyl sydnones carrying azido group were synthesized and subjected to react with a variety of alkenic and acetylenic dipolarophilic reagents; N-phenyl maleimide, phenyl vinyl sulfone, and phenyl propiolic acid. All the new products are identified by spectral/physical data including high-resolution mass measurements and X-ray diffraction data.
- Dürüst, Ya?ar,Y?ld?z, Elif,Karaku?, Hamza,Kariuki, Benson M.
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p. 660 - 670
(2017/03/24)
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- Expanding available pyrazole substitution patterns by sydnone cycloaddition reactions
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We report the use of alkynylsilanes for the regiocontrolled synthesis of pyrazoles from functionalised sydnones. The strategies outlined herein allow a range of pyrazoles to be accessed with substitution patterns that are otherwise not directly obtained with high selectivity by alkyne cycloadditions. Moreover, this study serendipitously highlighted a simple and convenient procedure for the synthesis of aryl monofluoromethyl ethers through the combination of TBAF and dichloromethane.
- Brown,Harrity
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p. 3160 - 3172
(2017/05/08)
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- Bioorthogonal Click and Release Reaction of Iminosydnones with Cycloalkynes
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We report the discovery of a new bioorthogonal click-and-release reaction involving iminosydnones and strained alkynes. This transformation leads to two products resulting from the ligation and fragmentation of iminosydnones under physiological conditions. Optimized iminosydnones were successfully used to design innovative cleavable linkers for protein modification, thus opening up new areas in the fields of drug release and target-fishing applications. This click-and-release technology offers the possibility of exchanging tags on proteins for functionalized cyclooctynes under mild and bioorthogonal conditions.
- Bernard, Sabrina,Audisio, Davide,Riomet, Margaux,Bregant, Sarah,Sallustrau, Antoine,Plougastel, Lucie,Decuypere, Elodie,Gabillet, Sandra,Kumar, Ramar Arun,Elyian, Jijy,Trinh, Minh Nguyet,Koniev, Oleksandr,Wagner, Alain,Kolodych, Sergii,Taran, Frédéric
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supporting information
p. 15612 - 15616
(2017/12/02)
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- Synthesis of aminopyrazoles from sydnones and ynamides
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Aminopyrazoles are prepared from readily accessible sydnones and sulfonyl ynamides using either a copper-mediated sydnone alkyne cycloaddition (CuSAC) or in situ generated strained cyclic ynamides.
- Wezeman,Comas-Barceló,Nieger,Harrity,Br?se
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supporting information
p. 1575 - 1579
(2017/02/23)
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- 4-Halogeno-sydnones for fast strain promoted cycloaddition with bicyclo-[6.1.0]-nonyne
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New sydnone derivatives have been synthesized and screened for their capacity to undergo fast copper-free cycloaddition reaction with bicyclo-[6.1.0]-nonyne. The influences of substitution in positions N-3 and C-4 of sydnones have been particularly studied leading to the identification of highly reactive partners for bio-orthogonal ligation reactions.
- Plougastel, Lucie,Koniev, Oleksandr,Specklin, Simon,Decuypere, Elodie,Créminon, Christophe,Buisson, David-Alexandre,Wagner, Alain,Kolodych, Sergii,Taran, Frédéric
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supporting information
p. 9376 - 9378
(2014/08/05)
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- One-pot synthesis of 1,4-disubstituted pyrazoles from arylglycines via copper-catalyzed sydnone-alkyne cycloaddition reaction
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A robust method for constructing 1,4-pyrazoles from arylglycines was developed using the copper-catalyzed sydnone-alkyne cycloaddition reaction. The procedure offers a straightforward and general route to the pyrazole heterocycle through a three-step one-pot procedure.
- Specklin, Simon,Decuypere, Elodie,Plougastel, Lucie,Aliani, Soifia,Taran, Frédéric
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p. 7772 - 7777
(2014/10/15)
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- Discovery of chemoselective and biocompatible reactions using a high-throughput immunoassay screening
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An immunoassay-based method was used to screen numerous combinations of dipoles and dipolarophiles for their ability to undergo chemoselective and biocompatible [3+2] cycloaddition reactions. The approach fulfills most of the requirements of the click concept and led to the discovery of a copper-catalyzed reaction that generates pyrazoles from sydnone and alkyne reagents. Copyright
- Kolodych, Sergii,Rasolofonjatovo, Evelia,Chaumontet, Manon,Nevers, Marie-Claire,Creminon, Christophe,Taran, Frederic
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supporting information
p. 12056 - 12060
(2013/12/04)
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- Regioselective reaction: Synthesis, characterization and pharmacological activity of some new Mannich and Schiff bases containing sydnone
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A novel series of 1-substituted aminomethyl-3-[1-(4-isobutylphenyl)ethyl]- 4-(3-aryl-4-sydnonylidene) amino-1,2,4-triazol-5-thiones (9), was prepared from the 3-[1-(4-isobutylphenyl)ethyl]-4-(3-aryl-4-sydnonylidene) amino 5-mercapto-1,2,4-triazoles (8) by aminomethylation with formaldehyde and secondary amine. The structures of Schiff bases (8) and Mannich bases (9) were characterized on the basis of IR, NMR, mass spectra1 data and elemental analysis. The newly synthesized compounds were screened for their anti-inflammatory and analgesic activities. Mannich bases (9) carrying piperidine and morpholine residues showed promising anti-inflammatory and analgesic activity.
- Nithinchandra,Kalluraya,Aamir,Shabaraya
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experimental part
p. 597 - 604
(2012/09/11)
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- Synthesis of 2 H-indazoles by the [3 + 2] dipolar cycloaddition of sydnones with arynes
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A rapid and efficient synthesis of 2H-indazoles has been developed using a [3 + 2] dipolar cycloaddition of sydnones and arynes. A series of 2H-indazoles have been prepared in good to excellent yields using this protocol, and subsequent Pd-catalyzed coupl
- Fang, Yuesi,Wu, Chunrui,Larock, Richard C.,Shi, Feng
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experimental part
p. 8840 - 8851
(2012/01/02)
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- Synthesis of 2H-indazoles by the [3 + 2] cycloaddition of arynes and sydnones
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A rapid and efficient synthesis of 2H-indazoles has been developed, which involves the [3 + 2] dipolar cycloaddition of arynes and sydnones. The process proceeds under mild reaction conditions in good to excellent yields.
- Wu, Chunrui,Fang, Yuesi,Larock, Richard C.,Shi, Feng
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supporting information; experimental part
p. 2234 - 2237
(2010/08/04)
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- Cross coupling of bromo sydnones: Development of a flexible route toward functionalized pyrazoles
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(Chemical Equation Presented) The application of a Suzuki cross coupling approach to a range of C-4 substituted sydnones from a 4-bromosydnone is described. Moreover, the potential of this approach to prepare a diverse range of pyrazoles is demonstrated.
- Browne, Duncan L.,Taylor, John B.,Plant, Andrew,Harrity, Joseph P. A.
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supporting information; experimental part
p. 396 - 400
(2009/04/07)
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- Convenient access to 1,3,4-trisubstituted pyrazoles carrying 5-nitrothiophene moiety via 1,3-dipolar cycloaddition of sydnones with acetylenic ketones and their antimicrobial evaluation
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Novel 1-aryl-3-(5-nitro-2-thienyl)-4-aroyl-pyrazoles 7 have been synthesized by the 1,3-dipolar cycloaddition of 3-arylsydnones 3 with 1-aryl-3-(5-nitro-2-thienyl)-2-propyn-1-ones 6. The newly synthesized compounds were well characterized by elemental analysis, IR, 1H NMR and mass spectral studies. They were also screened for their antibacterial and antifungal activities against a variety of microorganisms and the results of such studies have been discussed in this article.
- Satheesha Rai,Kalluraya, Balakrishna,Lingappa,Shenoy, Shaliny,Puranic, Vedavati G.
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p. 1715 - 1720
(2008/12/20)
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- Synthesis and evaluation of phenyl substituted sydnones as potential DPPH-radical scavengers
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A series of phenyl substituted sydnones has been synthesized and their radical-scavenging activity has been studied on DPPH free radical. Out of eighteen compounds screened, nine compounds show interesting activity. A mechanism is presented whereby sydnones scavenge DPPH radical through donating H-atom at 4th-position. Its strong radical-scavenging activity mainly arises from 1, 2, 3-oxadiazolium-5-olate ring. Different substituents and their positions on the phenyl ring differently influence DPPH scavenging activity and therefore, may provide clues to design and develop better free-radical scavenging sydnones with multiple activities.
- Mallur, Shanta G.,Tiwari,Raju, B. China,Babu, K. Suresh,Ali, A. Zehra,Sastry,Rao, J. Madhusudana
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p. 1686 - 1689
(2008/09/19)
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- One-pot conversion of N-arylglycines to sydnones efficiently promoted by bis-chlorine-1,4-diazabicyclo[2.2.2]octane complex Cl2-dabco in the presence of NaNO2/Ac2O under neutral condition
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Bis-chlorine-1,4-diazabicyclo[2.2.2]octane complex, (Cl2-DABCO), has been found as an active chlorine complex for effective one-pot conversion of various N-arylglycines to sydnones in high yields (85-95%) under mild and neutral condition.
- Azarifar, Davood,Ghasemnejad-Bosra, Hassan,Tajbaksh, Mahmood,Habibzadeh, Setareh
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p. 1815 - 1819
(2008/03/14)
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- Microwave-assisted synthesis of N-arylglycines: Improvement of sydnone synthesis
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Reactions of anilines with ethyl bromoacetate under microwave irradiation have afforded N-arylglycines that are subsequently converted to their N-nitroso derivatives with a combination of silica chloride or periodic acid, wet SiO2 and sodium nitrite in CH2Cl2 with satisfactory yields. In the final step, the use of 1,3-dibromo-5,5-dimethylhydantoin (DBH) as a new and effective reagent for dehydration of N-nitroso-N-arylglycines to sydnones was successfully examined.
- Azarifar, Davood,Bosra, Hassan Ghasemnejad,Zolfigol, Mohammad-Ali,Tajbaksh, Mahmood
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p. 175 - 181
(2007/10/03)
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- N,N,N′,N′-Tetrabromobenzene-1,3-disolfonamide (TBBDS) as an efficient promoter for one-pot conversion of N-arylglycines to sydnones in the presence of NaNO2/Ac2O under neutral conditions
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N,N,N′,N′-Tetrabromobenzene-1,3-disolfonamide (TBBDS)-promoted one-pot conversion of various N-arylglycines to sydnones using a combination of NaNO2 and Ac2O has been achieved efficiently through N-nitrosation followed by cyclization
- Azarifar, Davood,Ghasemnejad-Bosra, Hassan,Ghorbani-Vaghei, Ramin,Tajbaksh, Mahmood
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p. 2343 - 2347
(2007/10/03)
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- Catalytic activity of 1,3-dibromo-5,5-dimethylhydantoin (DBH) in the one-pot transformation of N-arylglycines to N-arylsydnones in the presence of NaNO2/Ac2O under neutral conditions: Subsequent bromination of these sydnones to their
-
1,3-Dibromo-5,5-dimethylhydantoin (DBH) has been found to efficiently catalyze the one-pot conversion of various N-arylglycines through N-nitrosation and cyclization to sydnones in combination with NaNO2 and Ac 2O in high yields (80-
- Azarifar, Davood,Ghasemnejad-Bosra, Hassan
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p. 1123 - 1126
(2007/10/03)
-
- 2-Chloro-1,3-dimethylimidazolinium chloride. 2. Its application to the construction of heterocycles through dehydration reactions
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2-Chloro-1,3-dimethylimidazolinium chloride (DMC) (1) can act as a powerful dehydrating equivalent to DCC (2) under nearly neutral conditions. Its application to the construction of heterocycles through dehydration reactions is described.
- Isobe, Toshio,Ishikawa, Tsutomu
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p. 6989 - 6992
(2007/10/03)
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- Reactions of 4-acetylsydnones with hydrazine: Formation of 2,4- dihydropyrol-3-ones
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Reactions of 4-acetylsydnones with hydrazine at room temperature yielded a series of 2,4-dihydropyrazol-3-ones. The cycloaddition via sydnone rings with loss of a nitrogen oxide ion is a new type of reaction for the application of sydnone in organic synth
- Tien, Hsien-Ju,Lin, Shaw-Tao,Yang, Mei-Lin
-
-
- Synthesis and reactions of 9,10-diazatetracyclo-[6.3.0.0.4,110.5.9]undecanes
-
The tandem 1,3-dipolar cycloaddition between sydnones and 1,5-cyclooctadiene provides 9,10-diazatetracyclo[6.3.0.0.4,110.5,9]undecanes (the Weintraub reaction) in modest to good yields.
- Gribble, Gordon W.,Hirth, Bradford H.
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p. 719 - 726
(2007/10/03)
-
- The Reaction of 4-Formylsydnone and Methyl Ketones
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In the presence of base, 3-substituted 4-formyl- and 4-acetylsydnones decarbonylated to afford the corresponding 3-substituted sydnones.The Claisen-Schmidt reaction occurred between 3-substituted 4-formylsydnones and methyl ketone (such as 4-acetylsydnone
- Hung, Wei-Jing,Tien, Hsien-Ju,Chou, Tzoo-Ming,Tien, Ling-Ling,Wu, Cheng-Kwei
-
p. 385 - 392
(2007/10/02)
-
- DEBROMINATION OF 4-BROMO-3-ARYLSYDNONES WITH SODIUM SULFITE
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4-Bromo-3-arylsydnones 1 are debrominated to the corresponding 3-arylsydnones 2 in good to excellent yield using sodium sulfite in methanol/water.In contrast to previously employed reagents, the reaction is successful in the presence of electron-donating,
- McChord, K. L.,Tullis, S. A.,Turnbull, K.
-
p. 2249 - 2253
(2007/10/02)
-
- The Efficient Synthesis of 3-Arylsydnones Under Neutral Conditions
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Various substituted aryl sydnones can be prepared in high yield under mild, neutral conditions by nitrosation of the appropriate aryl glycine with isoamyl nitrite in dimethoxyethane followed by cyclization with trifluoroacetic anhydride.
- Applegate, Jacqueline,Turnbull, Kenneth
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p. 1011 - 1012
(2007/10/02)
-
- DEBROMINATION OF 4-BROMO-3-ARYLSYDNONES WITH SODIUM DITHIONITE.
-
A variety of 4-bromo-3-arylsydnones can be debrominated with sodium dithionite in excellent yield under very mild conditions.
- Turnbull, K.,Saljoughian, M.
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p. 461 - 466
(2007/10/02)
-
- Debromination of 3-Aryl-4-bromosydnones with Sodium Borohydride
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Debromination of 4-bromo-3-(2-substituted aryl) sydnones 1 with sodium borohydride in methanol occurs readily to give good yields of the corresponding parent sydnones 2, except in those cases where the aryl substituent also reacts.The utility of the proce
- Turnbull, Kenneth
-
p. 334 - 336
(2007/10/02)
-
- Sydnones, III. 4-Sydnonylsilanes
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Silylation of 4-sydnonyllithium compounds with chlorosilanes leads to 4-sydnonylsilanes (3a-d, 5d). 5d and other bis(4-sydnonyl)silanes can also be prepared preferably by "trans-silation reaction".
- Dickopp, Heinz
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p. 1830 - 1836
(2007/10/02)
-