2258-42-6Relevant articles and documents
Synthesis of benzannulated N-heterocyclic carbene ligands by a template synthesis from 2-nitrophenyl isocyanide
Hahn, F. Ekkehardt,Plumed, Cesar Garcia,Muender, Marco,Luegger, Thomas
, p. 6285 - 6293 (2004)
The reaction of 2-nitrophenyl isocyanide 2 with [M(CO)5(thf)] (M = Cr, Mo, W) yields the isocyanide complexes [M(CO)5(2)] (3: M = Cr; 4: M = Mo; 5: M = W). Complexes 3-5 react with elemental tin under reduction of the nitro function of the isocyanide ligand to give the complexes with the unstable 2-aminophenyl isocyanide ligand. The coordinated 2-aminophenyl isocyanide ligand in all three complexes reacts spontaneously under intramolecular nucleophilic attack of the primary amine at the isocyanide carbon atom to yield the complexes with the NH,NH-benzimidazol-2-ylidene ligand (6: M = Cr; 7: M = Mo; 8: M = W). An incomplete reduction of the nitro group in 3-5 is observed when hydrazine hydrate is used instead of tin. Here the formation of complexes with a coordinated 2-hydroxylamine-functionalized phenyl isocyanide [(CO)5M-CN-C6H4--2-N(H)-OH] is postulated and this unstable ligand again undergoes intramolecular cyclization to give the NH,NOH-stabilized benzimidazol-2-ylidene complexes 9-11. The tungsten derivative 11 can be allylated stepwise by a deprotonation/ alkylation sequence first at the OH and then at the NH position to yield the monoallylated and diallylated species 12 and 13. The molecular structures of 3-5 and 12-13 were established by X-ray crystallography.
Kinetic and mechanistic study of the atmospheric oxidation by OH radicals of allyl acetate
Picquet-Varrault,Fittschen,Doussin,Durand-Jolibois,Pirali,Carlier
, p. 4081 - 4086 (2002)
A potential source of acetates, including allyl acetate, is combustion of esterified rape oil used as substitution fuel. This new formulation of diesel fuel significantly reduces the emission of particulate matter. To better evaluate the environmental impact of acetates, OH-induced oxidation kinetic and mechanism of allyl acetate were studied at room temperature and 1 atm using three environmental chambers (an indoor Teflon-film bag, an indoor Pyrex photoreactor, and the outdoor smog chamber EUPHORE. The main oxidation products were acetoxyacetaldehyde and formaldehyde. A mechanism was developed to describe the OH-induced oxidation of the acetate in the presence of NOx. Reaction with OH radicals was the main tropospheric fate of allyl acetate. When it reacted with OH radicals, it could contribute to the formation of photooxidants close to the emission sources. Acetoxyacetaldehyde yield was slightly smaller in the experiment at low NOx since some peroxides could be produced from peroxy radical + HO2 reaction and compete with the acetoxyacetaldehyde production.
Total synthesis of (±)-welwitindolinone A isonitrile
Reisman, Sarah E.,Ready, Joseph M.,Hasuoka, Atsushi,Smith, Catherine J.,Wood, John L.
, p. 1448 - 1449 (2006)
A highly stereoselective total synthesis of the alkaloid natural product welwitindolinone A isonitrile has been completed. The synthesis utilizes a chloronium ion mediated semi-pinacol rearrangement to simultaneously install the C10 quaternary center and neopentyl chlorine and a novel anionic cyclization to construct the spiro-oxindole with complete stereocontrol. Copyright
Diversity oriented synthesis: Concise entry to novel derivatives of Yohimbine and Corynanthe alkaloids
Wang, Zhiqian,Kaneda, Kyosuke,Fang, Zhenglai,Martin, Stephen F.
, p. 477 - 479 (2012)
A novel MCAP-cycloaddition sequence has been applied to the facile synthesis of β-carboline intermediates to gain rapid access to novel derivatives of Yohimbine-like and Corynanthe-like compounds that may be easily diversified by cross-coupling reactions
Linear 6,6′-biazulenyl framework featuring isocyanide termini: Synthesis, structure, redox behavior, complexation, and self-assembly on Au(111)
Maher, Tiffany R.,Spaeth, Andrew D.,Neal, Brad M.,Berrie, Cindy L.,Thompson, Ward H.,Day, Victor W.,Barybin, Mikhail V.
, p. 15924 - 15926 (2010)
The key step in accessing the title species (5), the first nonbenzenoid diisocyanobiaryl, involved an unexpected homocoupling of a 6-bromoazulene derivative. The reversible 2e- reduction of 5 was addressed electrochemically and computationally. The shifts in energies of the S 0→S1 and S0→S2 transitions for a series of related 6,6′-biazulenyl derivatives correlate with the e--donating/-withdrawing strength of their 2,2′-substituents but follow opposite trends. Species 5 adsorbs end-on (η1) to the Au(111) surface via one of its -NC groups to form a 2-nm-thick film. In addition, bimetallic coordination of 5's -NC termini can be readily achieved.
Welwitindolinone C synthetic studies. Construction of the welwitindolinone carbon skeleton via a transannular nitrone cycloaddition
Freeman, David B.,Holubec, Alexandra A.,Weiss, Matthew W.,Dixon, Julie A.,Kakefuda, Akio,Ohtsuka, Masami,Inoue, Munenori,Vaswani, Rishi G.,Ohki, Hidenori,Doan, Brian D.,Reisman, Sarah E.,Stoltz, Brian M.,Day, Joshua J.,Tao, Ran N.,Dieterich, Noah A.,Wood, John L.
, p. 6647 - 6655 (2010)
Described is the construction of the N-methylwelwitindolinone C core via an efficient strategy that employs a sequential rhodium carbenoid-mediated O-H insertion, Claisen rearrangement and transannular [3+2] nitrone cycloaddition.
Reactions of OH and Cl with isopropyl formate, isobutyl formate, n-propyl isobutyrate and isopropyl isobutyrate
Zhang,Liang,Jiang,Cazaunau,Da?le,Mu,Mellouki
, p. 68 - 74 (2014)
The rate coefficients for the reactions of OH with isopropyl formate, isobutyl formate, n-propyl isobutyrate and isopropyl isobutyrate have been determined using both absolute and relative methods. The relative rate method has been also used to measure the room temperature rate coefficient for the reaction of Cl with the same esters. In addition, a series of runs conducted on the OH-initiated oxidation of isopropyl formate, isobutyl formate and n-propyl isobutyrate showed the formation of acetone from the three reactions. The formation of propanal was also observed for n-propyl isobutyrate.
An efficient approach to the stereocontrolled synthesis of enamides
Villa, Mathew V. J.,Targett, Sarah M.,Barnes, John C.,Whittingham, William G.,Marquez, Rodolfo
, p. 1631 - 1633 (2007)
A fast, flexible, and efficient approach for the stereocontrolled synthesis of enamides has been developed starting from lactams and amides through the use of imides. This new approach provides access to enamide systems not easily or currently accessible through other approaches.
Coordination-Driven Self-Assembly of Cyclometalated Iridium Squares Using Linear Aromatic Diisocyanides
Olumba, Morris E.,Na, Hanah,Friedman, Alan E.,Teets, Thomas S.
, p. 5898 - 5907 (2021)
Here, we demonstrate facile [4 + 4] coordination-driven self-assembly of cyclometalated iridium(III) using linear aryldiisocyanide bridging ligands (BLs). A family of nine new [Ir(C^N)2(μ-BL)]44+ coordination cages is described, where C^N is the cyclometa
A novel synthesis of substituted 3-amino and 3-thio pyrimido[5,4-e]-1,2,4-triazine-5,7(1H,6H)-diones
Xu, Hao,Powelson, Ian A.,Jin, Yafei,Showalter, Hollis D.
, p. 1690 - 1694 (2021)
Fervenulin is a natural product that has been extensively studied due to its molecular features and breadth of biological activities. Published studies have reported the generation of numerous analogues of the bicyclic pyrimidotriazinodione core. One underrepresented subclass are compounds with electron releasing atoms bonded directly to the C-3 position. We report an efficient and straightforward synthesis of compounds with substituted amino and thio functionality attached to the C-3 position. These are derived from a common 3-chloro precursor that is made in six steps in 15.8% overall yield from a starting chlorouracil. Our methodology should be applicable to the synthesis of C-3 ether congeners also, and through previously described chemistry be expandable to incorporating diversity at the N-6 position of the pyrimidotriazinodione core. The chemistry reported herein expands possibilities for the generation of diverse libraries of substituted pyrimidotriazinediones for future studies.
