508191-77-3Relevant articles and documents
Water-Involved Ring-Opening of 4-Phenyl-1,2,4-triazoline-3,5-dione for “Photo-Clicked” Access to Carbamoyl Formazan Photoswitches In Situ
Zheng, Yuanqin,Zhou, Yuqiao,Zhang, Yan,Deng, Pengchi,Zhao, Xiaohu,Jiang, Shichao,Du, Guangxi,Shen, Xin,Xie, Xinyu,Su, Zhishan,Yu, Zhipeng
supporting information, (2021/12/22)
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.
Exploiting Synergistic Catalysis for an Ambient Temperature Photocycloaddition to Pyrazoles
Lakeland, Christopher P.,Watson, David W.,Harrity, Joseph P. A.
supporting information, p. 155 - 159 (2019/12/11)
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.
Mechanosynthesis of sydnone-containing coordination complexes
Pétry, Nicolas,Vanderbeeken, Thibaut,Malher, Astrid,Bringer, Yoan,Retailleau, Pascal,Bantreil, Xavier,Lamaty, Frédéric
, p. 9495 - 9498 (2019/08/15)
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.
Anionic N-heterocyclic carbenes by decarboxylation of sydnone-4-carboxylates
Lücke, Ana-Luiza,Wiechmann, Sascha,Freese, Tyll,Nieger, Martin,F?ldes, Tamás,Pápai, Imre,Gjikaj, Mimoza,Adam, Arnold,Schmidt, Andreas
, p. 2092 - 2099 (2018/03/26)
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
Sydnone Reporters for Highly Fluorogenic Copper-Free Click Ligations
Favre, Camille,De Cremoux, Lucie,Badaut, Jerome,Friscourt, Frédéric
, p. 2058 - 2066 (2018/02/23)
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.
Synthesis and crystal structure of 4-trifluoroacetyl-3-phenylsydnone
Kawase, Masami,Saijo, Ryosuke,Mori, Shigeki,Uno, Hidemitsu
, p. 2103 - 2110 (2017/11/21)
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.
Novel sydnone derivatives carrying azidomethyl-1,2, 4-oxadiazole unit and their 1,3-dipolar cycloadditions
Dürüst, Ya?ar,Y?ld?z, Elif,Karaku?, Hamza,Kariuki, Benson M.
, p. 660 - 670 (2017/03/24)
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.
Expanding available pyrazole substitution patterns by sydnone cycloaddition reactions
Brown,Harrity
, p. 3160 - 3172 (2017/05/08)
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.
Bioorthogonal Click and Release Reaction of Iminosydnones with Cycloalkynes
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
supporting information, p. 15612 - 15616 (2017/12/02)
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.
Synthesis of aminopyrazoles from sydnones and ynamides
Wezeman,Comas-Barceló,Nieger,Harrity,Br?se
supporting information, p. 1575 - 1579 (2017/02/23)
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.
