42574-02-7Relevant academic research and scientific papers
COMPOSITIONS AND METHODS FOR QUADRICYCLANE MODIFICATION OF BIOMOLECULES
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Paragraph 0306, (2013/09/26)
The present disclosure features a strain-promoted [2+2+2] reaction that can be carried out under physiological conditions. In general, the reaction involves reacting a pi-electrophile with a low lying LUMO with a quadricyclane on a biomolecule, generating
A bioorthogonal quadricyclane ligation
Sletten, Ellen M.,Bertozzi, Carolyn R.
supporting information; experimental part, p. 17570 - 17573 (2012/01/04)
New additions to the bioorthogonal chemistry compendium can advance biological research by enabling multiplexed analysis of biomolecules in complex systems. Here we introduce the quadricyclane ligation, a new bioorthogonal reaction between the highly strained hydrocarbon quadricyclane and Ni bis(dithiolene) reagents. This reaction has a second-order rate constant of 0.25 M-1 s-1, on par with fast bioorthogonal reactions of azides, and proceeds readily in aqueous environments. Ni bis(dithiolene) probes selectively labeled quadricyclane-modified bovine serum albumin, even in the presence of cell lysate. We have demonstrated that the quadricyclane ligation is compatible with, and orthogonal to, strain-promoted azide-alkyne cycloaddition and oxime ligation chemistries by performing all three reactions in one pot on differentially functionalized protein substrates. The quadricyclane ligation joins a small but growing list of tools for the selective covalent modification of biomolecules.
Free radical reaction of diisopropyl xanthogen disulfide with unsaturated systems
Gareau, Yves,Beauchemin, Andre
, p. 2003 - 2017 (2007/10/03)
1,3-Dithiol-2-ones are prepared in one pot reaction from commercially available diisopropyl xanthogen disulfide (2) and alkynes under radical conditions. The 5-membered heterocycle is formed via a ring closure of vinyl radical (7) resulting from the thio radical addition of 5 to an alkyne. The reaction worked best for alkynes conjugated with a C=C double bond. The oxygen atoms of reagent (2) could be replaced by sulfur and this new reagent furnished 1,3-dithiol-2-thiones under radical conditions.
Photochemical Reactions of Phenylacetylenes with Ethylene Trithiocarbonate. Synthesis of Phenyl-substituted 2-Thioxo-1,3-dithioles
Yamada, Shuzo,Mino, Norihisa,Nakayama, Noboru,Ohashi, Mamoru
, p. 2497 - 2499 (2007/10/02)
A novel photochemical synthetic route to phenyl-substituted 2-thioxo-1,3-dithioles (TDT), intermediates in the synthesis of tetrathiafulvalenes (TTF), starting from ethylene trithiocarbonate (ETC) and phenylacetylenes is described.Phenyl and diphenyl-acetylene and 1-phenylpropyne reacted with ETC derivatives in reasonable yields.The fluorescence of the acetylenes was quenched by ETC via a trivial process: sensitization with benzophenone and quenching with air suggested that the reaction proceed mainly through the triplet excited states of the acetylenes.Irradiation of ETC alone with light of longer wavelength and quenching experiments suggested that the excited singlet state of ETC also participated in the reaction, in a minor process.
Comparison of the Thermal, Photochemical, and Mass Spectrometric Fragmentation of Sulphur Heterocycles with cis-Dithioethene-Structure
Fanghaenel, E.,Poleschner, H.
, p. 1 - 13 (2007/10/02)
The mass spectrometric primary fragmentation of 3-methylthio-1,4,2-dithiazines 1, 1,4-dithiins 2, 2,3-dihydro-1,4-dithiin-2-ones 4, 1,3-dithiole-2-ones 5, 2-imino-1,3-dithioles 6 and 1,3-dithiole-2-thiones 7 is compared with their thermolytical and photochemical reaction.In the mass spectra an intense peak of the dithiete radical ion is observed, if in the compounds an energetically favourable neutral molecule is preformed: in 1 methyl rhodanide, in 3 ethene, in 4 ketene, in 5 carbon monoxide and in 6 hydrogen cyanide.The substances 1, 3-6 - with the restriction by 3 - yield photochemically the dithiete, too.The photolysis of dithiazines 1 is wave length dewpendent.Mass spectrometrically, thermally and photochemically the dithiins 2 form thiophenes.The dithiolethiones 7 decompose mass spectrometrically and thermally into carbon disulfide, sulfur and ethynes, but photochemically they form tetrathiafulvalenes.The fragmentation of the compounds 1-6 is analogous in mass spectrometry and photolysis; 2, 3, 5 and with reservation 1 show similar mass spectrometric, thermal and photochemical reactivity.Posible reasons for these analogies are discussed.The dithietes, generated by photolysis of the compounds 1, 4, 5 or 6 react with iron penta-, nickel tetra-, molybdenum hexa- and tungsten hexacarbonyl in the preparative scale to the corresponding dithiolene complexes.
