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791-28-6Relevant articles and documents
Ketenimine and imine functions linked by an ethylene group. Intramolecular [4+2] cycloadditions leading to imidazo[1,2-b]isoquinolines
Alajarín, Mateo,Vidal, Angel,Tovar, Fulgencio,Sánchez-Andrada, Pilar,Bautista, Delia
, p. 9913 - 9918 (2003)
The intramolecular cyclization of imino-ketenimines where an ethylene or propylene chain is linking the nitrogen atoms of both functionalities is studied. The propylene tethered imino-ketenimines remain unchanged under thermal conditions, whereas their ethylene counterparts undergo a formal [4+2] cycloaddition, in which the ketenimine function acts as all-carbon diene and the imine as dienophile, to yield imidazo[1,2-b]isoquinolines. An X-ray crystal structure determination reveals that these cycloadducts incorporate an hydroxyl group at the benzylic carbon C10.
Examination of oxygen atom transfer reactivity of heteroscorpionate dioxo-Mo(VI) complexes: Geometric isomers, solvent effect, intermediates, and catalytic oxidation
Tran, Ba L.,Arita, Amy,Cooksy, Andrew L.,Carrano, Carl J.
, p. 45 - 51 (2016)
Heteroscorpionate-based [(L10O)MoO2Cl] and [(L3S)MoO2Cl] complexes containing an interchangeable third heteroatom donor have been utilized for the systematic investigation of oxygen atom transfer (OAT) reactivity. The detection of phosphoryl intermediates and products in the reaction pathway were probed by UV-Vis, mass spectrometry, and 31P NMR spectroscopy. The OAT reactivity of the metal complexes toward PPh3 were monitored by UV-Vis spectroscopy under pseudo-first order conditions. The sterically encumbered (L10O) ligand gives rise to isolable trans and cis isomers of [(L10O)MoO2Cl] allowing investigation into the role of geometry on OAT reactivity. The OAT reactivity of the cis isomer of (L10O)MoO2Cl demonstrated a dramatic solvent dependence, in which the reaction proceeded at a measureable rate only in pyridine. However, the trans counterpart reacted in all solvents and at much faster rates. The catalytic oxidation of PPh3 to OPPh3 by trans-[(L10O)MoO2Cl] and cis-[(L3S)MoO2Cl] complexes using DMSO as an oxygen donor was monitored by 31P NMR in DMF at 30 °C with rates, kcat = 4.26 × 10-5 s-1 and 5.28 × 10-5 s-1, respectively.
Reactive Oxygen Species (ROS)-vs Peroxyl-Mediated Photosensitized Oxidation of Triphenylphosphine: A Comparative Study
Bonesi, Sergio Mauricio,Protti, Stefano,Albini, Angelo
, p. 11678 - 11685 (2016)
The oxidation of triphenylphosphine in the presence of various photocatalytic systems (dicyanoanthracene/biphenyl, N-methylquinolinium, triphenylpyrylium, and thiatriphenylpyrylium tetrafluoroborate) was investigated by means of both steady state and lase
Regioselective Palladium-Catalyzed Heterocyclization-Sonogashira Coupling Cascades from 2-Alkynylbenzamides and Terminal Alkynes: Experimental and DFT Studies
Cruz, Francisco,Vaz, Belén,Vilar, Unai,Ortega, Aitor,Madich, Youssef,álvarez, Rosana,Aurrecoechea, José M.
, p. 3813 - 3826 (2018)
A regioselective heterocyclization-Sonogashira coupling cascade between 2-alkynylbenzamides and terminal alkynes is described. The reaction proceeds under Pd(II) catalysis, with air used as a terminal oxidant to regenerate the catalyst from the Pd(0) produced in the C-C coupling. The cascade process provides alkynyl-substituted isobenzofuranimine products in a single operation. These products are the result of a 5-exo O-cyclization, while products derived from the alternative 6-endo cyclization mode are observed in minor amounts. Two competing mechanisms have been considered to account for the observed results. Both involve heterocyclization, alkyne C-H activation, and reductive elimination steps but differ in the relative order of the first two. Control experiments using a preformed alkynylpalladium complex have shown that a mechanism starting with alkyne C-H activation is viable. On the other hand, DFT calculations indicate that the alternative cyclization-first mechanism is also competitive, particularly when PPh3 is used as ligand. Calculations also suggest that the exo cyclization is favored over the endo mode by the presence of PPh3 and σ-C Pd ligands in the activated complex undergoing cyclization.
Nucleophilic addition of azoles to triphenyl-(phenylethynyl)phosphonium bromide and base hydrolysis of the addition products
Bagdasaryan,Pogosyan,Panosyan,Asratyan,Indzhikyan
, p. 1324 - 1326 (2006)
Reactions of pyrazole, 3,5-dimethylpyrazole, imidazole, and 1,2,4-triazole with triphenyl(phenylethynyl)phosphonium bromide gave the corresponding 2-azolyl-2-phenylethenyl(triphenyl)phosphonium salts. Base hydrolysis of the addition products led to the formation of 2-azolyl-1,2-diphenylethyl(diphenyl) phosphine oxides. Nauka/Interperiodica 2006.
NOVEL RHODIUM DIOXYGEN COMPLEXES. REACTION OF THE DIOXYGEN LIGAND WITH THE COORDINATED OLEFIN
Sugimoto, Ryuichi,Suzuki, Hiroharu,Moro-Oka, Yoshihiko,Ikawa, Tsuneo
, p. 1863 - 1866 (1982)
Novel dinuclear rhodium dioxygen complexes having olefinic ligand are prepared by the reaction of cationic rhodium diene complexes, +Y- or +Y- (Y- = BF4su
Interaction of 4,5-diphenyl-2,3-dihydro-2,3-pyrroledione with ethoxycarbonylmethylenetriphenylphosphorane: synthesis and crystal srtucture of 4,5-diphenyl-Z-2-ethoxycarbonylmethylene-2,3-dihydro-3-pyrrolone
Aliev, Z. G.,Maslivets, A. N.,Simonchik, O. L.,Konyukhova, T. G.,Andreichikov, Yu. S.,Atovmyan, L. O.
, p. 1496 - 1498 (1995)
1-Unsubstituted 4,5-diphenyl-2,3-dihydro-2,3-pyrroledione interacts with ethoxycarbonylmethylenetriphenylphosphorane regioselectively to give 4,5-diphenyl-Z-2-ethoxycarbonylmethylene-2,3-dihydro-3-pyrrolone.The crystal and molecular structure of the latter was studied ny X-ray analysis. - Keywords: 2,3-dihydro-2,3-pyrroledione, alkoxycarbonylmethylenetriphenylphosphorane, Wittig reaction, crystal and molecular structure
Solvent Effect on Photooxidation of Triphenylphosphine Selenide Sensitized by Polymer-supported Rose Bengal
Tamagaki, Seizo,Akatsuka, Ryuji
, p. 3037 - 3038 (1982)
Solvent effect on the photooxygenation of triphenylphosphine selenide was examined by using cross-linked polystyrene- or silica gel-anchored Rose Bengal as sensitizers.Different types of solvent dependency of the product yields were observed in each case.
Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity
Corcos, Amanda R.,Villanueva, Omar,Walroth, Richard C.,Sharma, Savita K.,Bacsa, John,Lancaster, Kyle M.,MacBeth, Cora E.,Berry, John F.
, p. 1796 - 1799 (2016)
Bimetallic (Et4N)2[Co2(L)2], (Et4N)2[1] (where (L)3- = (N(o-PhNC(O)iPr)2)3-) reacts with 2 equiv of O2 to form the monometallic species (Et4N)[Co(L)O2], (Et4N)[3]. A crystallographically characterized analog (Et4N)2[Co(L)CN], (Et4N)2[2], gives insight into the structure of [3]1-. Magnetic measurements indicate [2]2- to be an unusual high-spin CoII-cyano species (S = 3/2), while IR, EXAFS, and EPR spectroscopies indicate [3]1- to be an end-on superoxide complex with an S = 1/2 ground state. By X-ray spectroscopy and calculations, [3]1- features a high-spin CoII center; the net S = 1/2 spin state arises after the Co electrons couple to both the O2?- and the aminyl radical on redox non-innocent (L?)2-. Dianion [1]2- shows both nucleophilic and electrophilic catalytic reactivity upon activation of O2 due to the presence of both a high-energy, filled O2- π? orbital and an empty low-lying O2- π? orbital in [3]1-.
Synthesis of fluorophosphoranes via the mitsunobu reaction
Harvey, Peta J.,Jenkins, Ian D.
, p. 9775 - 9778 (1994)
Treatment of triphenylphosphine with potassium hydrogen fluoride or hydrogen fluoridepyridine and diisopropyl azodicarboxylate in acetonitrile or tetrahydrofuran, at room temperature results in the clean formation of difluorotriphenylphosphorane. Analogous results were obtained with other phosphines such as tributylphosphine and tris(dimethylamino) phosphine.
