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1823-91-2Relevant academic research and scientific papers
Synthesis of alkylaryl-and diarylnitriles from ketones via N-(1- arylalkylidene)-cyanomethyl amines
Selva, Maurizio,Bomben, Andrea,Tundo, Pietro
, p. 1561 - 1569 (1999)
Alkylaryl- and diarylketones (Arcor; R= alkyl, aryl, 1) can be converted into nitriles [ArCH(CN)R, 2] containing an additional carbon atom through a base-promoted reaction of N-(1-arylalkylidene)-cyanomethyl amines [ArC(=NCH2CN)R, 3].
Studies on Transition-metal Cyano-complexes. Part 4. Cyanide Hydride Complexes of Groups 6A and 8
Mockford, M. Jane,Griffith, William P.
, p. 717 - 722 (1985)
The new complex K4*2H2O and its characterisation by 1H, 13C n.m.r. and vibrational spectra are reported.Vibrational and n.m.r. data are also presented for 3- (M = Rh or Ir).Attempts to prepare other cyanide hydride species ar
Iridium-catalyzed selective C-C bond cleavage of nitriles and ketones
Terai, Hiroki,Takaya, Hikaru,Murahashi, Shun-Ichi
, p. 2185 - 2187 (2004)
Selective and catalytic C-C bond cleavage of pentanedinitriles and 5-oxohexanenitriles can be performed in the presence of iridium hydride complex IrH5(Pi-Pr3)2 (1). The key steps of this reaction are α-C-H activation of t
Activation of nitriles by metal ligand cooperation. reversible formation of ketimido- and enamido-rhenium PNP pincer complexes and relevance to catalytic design
Vogt, Matthias,Nerush, Alexander,Iron, Mark A.,Leitus, Gregory,Diskin-Posner, Yael,Shimon, Linda J. W.,Ben-David, Yehoshoa,Milstein, David
, p. 17004 - 17018 (2013)
The dearomatized complex cis-[Re(PNPtBu*)(CO)2] (4) undergoes cooperative activation of Ci - N triple bonds of nitriles via [1,3]-addition. Reversible C-C and Re-N bond formation in 4 was investigated in a combined experimental and c
Lewis acid controlled regioselectivity in styrene hydrocyanation
Bini, Laura,Pidko, Evgeny A.,Mueller, Christian,Van Santen, Rutger A.,Vogt, Dieter
, p. 8768 - 8778 (2009)
According to present knowledge, the Ni-catalyzed hydrocyanation of styrene leads predominantly to the branched product 2-phenylpropionitrile (98%). We observed a dramatic inversion of the regioselectivity upon addition of a Lewis acid. Up to 83 % of the l
Convenient transformation of optically active nitroalkanes into chiral aldoximes and nitriles
Czekelius, Constantin,Carreira, Erick M.
, p. 612 - 615 (2005)
An environmentally friendly reaction that excludes the potential contamination of the products by metal impurities is reported. In this reaction, optically active aldoximes and nitriles are prepared from chiral nitroalkanes (see scheme). The methodology described expands the possibilities available for the conversion of nitroalkanes into valuable targets.
Coupling of the Decarboxylation of 2-Cyano-2-phenylpropanoic Acid to Large-Amplitude Motions: A Convenient Fuel for an Acid-Base-Operated Molecular Switch
Berrocal, José Augusto,Biagini, Chiara,Mandolini, Luigi,Di Stefano, Stefano
, p. 6997 - 7001 (2016)
The decarboxylation of 2-cyano-2-phenylpropanoic acid is fast and quantitative when carried out in the presence of 1?molar equivalent of a [2]catenane composed of two identical macrocycles incorporating a 1,10-phenanthroline unit in their backbone. When decarboxylation is over, all of the catenane molecules have experienced large-amplitude motions from neutral to protonated catenane, and back again to the neutral form, so that they are ready to perform another cycle. This study provides the first example of the cyclic operation of a molecular switch at the sole expenses of the energy supplied by the substrate undergoing chemical transformation, without recourse to additional stimuli. Poetry in motion: Carboxylic acid 1 was found to be a convenient fuel for the operation of a molecular switch that moves under the influence of protonation-deprotonation steps. The cyclic motions of the catenane switch were induced solely by the chemical energy supplied by the decarboxylation of 1, without recourse to additional stimuli.
Cyanide-free enantioselective synthesis of nitriles: Synthetic proof of a biocatalytic concept and mechanistic insights
Metzner, Richard,Okazaki, Seiji,Asano, Yasuhisa,Gr?ger, Harald
, p. 3105 - 3109 (2014)
The first ( by definition ) cyanide-free enantioselective synthetic approach towards chiral α - and β -branched nitriles is reported. This process is based on a biocatalytic dehydration of racemic aldoximes by using an aldoxime dehydratase and proceeds with high conversion and excellent enantioselectivity (up to 98% ee) with water as the only side-product when starting from a racemic substrate with a high E/Z ratio. Thus, in combination with the facile generation of aldoximes through condensation of readily accessible aldehydes with hydroxylamine, this methodology offers an attractive and efficient path to chiral nitriles with excellent atom economy in aqueous solution. Furthermore, this study shows a surprising enzymatic dependency of the enantiopreference on the E or Z configuration of the aldoxime moiety. Notably, the whole stereochemical course of this enzymatic reaction has been rationalized by means of a computational study.
Two Faces of the Same Coin: Coupling X-Ray Absorption and NMR Spectroscopies to Investigate the Exchange Reaction Between Prototypical Cu Coordination Complexes
Busato, Matteo,Cenesi, Flavia,D'Angelo, Paola,Del Giudice, Daniele,Di Berto Mancini, Marika,Di Stefano, Stefano,Frateloreto, Federico,Lanzalunga, Osvaldo,Oliveira De Souza, Danilo,Tavani, Francesco
supporting information, (2021/12/22)
The satisfactory rationalization of complex reactive pathways in solution chemistry may greatly benefit from the combined use of advanced experimental and theoretical complementary methods of analysis. In this work, we combine X-Ray Absorption and 1H NMR spectroscopies with state-of-the-art Multivariate Curve Resolution and theoretical analyses to gain a comprehensive view on a prototypical reaction involving the variation of the oxidation state and local structure environment of a selected metal ion coordinated by organic ligands. Specifically, we investigate the 2-cyano-2-phenylpropanoic acid reduction of the octahedral complex established by the Cu2+ ion with terpyridine to the tetrahedral complex formed by Cu+ and neocuproine. Through our interdisciplinary approach we gain insights into the nature, concentration time evolution and structures of the key metal (XAS measurements) and organic (1H NMR measurements) species under reaction. We believe our method may prove to be useful in the toolbox necessary to understand the mechanisms of reactive processes of interest in solution.
Iodine Promoted Conversion of Esters to Nitriles and Ketones under Metal-Free Conditions
Xiao, Jing,Guo, Fengzhe,Li, Yinfeng,Li, Fangshao,Li, Qiang,Tang, Zi-Long
, p. 2028 - 2035 (2021/02/03)
We report a novel strategy to prepare valuable nitriles and ketones through the conversion of esters under metal-free conditions. By using the I2/PCl3 system, various substrates including aliphatic and aromatic esters could react with acetonitrile and arenes to afford the desired products in good to excellent yields. This method is compatible with a number of functional groups and provides a simple and practical approach for the synthesis of nitrile compounds and aryl ketones.
