18176-72-2Relevant articles and documents
Semiconductor Photocatalysis: Reaction Mechanisms for the Photoreductive cis-trans Isomerization of Electron-Deficient Alkenes Catalyzed by CdS Powder
Shiragami, Tsutomu,Fukami, Shinako,Pac, Chyongjin,Wada, Yuji,Yanagida, Shozo
, p. 2461 - 2466 (1993)
Highly pure commercially available CdS powder (99.999percent) catalyzes the effective cis-trans photoisomerization of electron-deficient alkenes under visible light irradiation using triethylamine (TEA) as an electron donor, accompanying the formation of the dihydro compound as a two-electron reduction product.The photoisomerization does not occur at all in the absence of TEA.Donor effect, solvent effect, deuterium incorporation experiments for photocatalysis, and MOPAC molecular orbital calculation (MNDO/PM3) of the intermediary radical anions from the alkenes were investigated in order to elucidate the mechanism of this photoisomerization.These results reveal that the CdS-catalyzed cis-trans photoisomerization should proceed through two pathways involving the photoreduction of alkenes: one through the back electron transfer from the radical anion of the alkene (alkene radical anion) towards the radical cation of TEA (TEA radical cation), both formed by photoexcited conduction band electrons and holes of CdS, respectively.The other is the reoxidation of a radical intermediate (alkyl radical), formed by protonation of alkene radical anion, by TEA radical cation.
Electrochemical Tandem Olefination and Hydrogenation Reaction with Ammonia
Zhang, Xiaofeng,Jiang, Runze,Cheng, Xu
, p. 16016 - 16025 (2021/08/24)
An electrochemical Horner-Wadsworth-Emmons/hydrogenation tandem reaction was achieved using ammonia as electron and proton donors. The reaction could give two-carbon-elongated ester and nitrile from aldehyde or ketones directly. This reaction could proceed with a catalytic amount of base or even without a base. The ammonia provides both the electron and proton for this tandem reaction and enables the catalyst-free hydrogenation of an α,β-unsaturated HWE intermediate. More than 40 examples were reported, and functional groups, including heterocycles and hydroxyl, were tolerated.
Nickel-Catalyzed Deaminative Cyanation: Nitriles and One-Carbon Homologation from Alkyl Amines
Xu, Jianyu,Twitty, J. Cameron,Watson, Mary P.
supporting information, p. 6242 - 6245 (2021/08/23)
A nickel-catalyzed deaminative cyanation of Katritzky pyridinium salts has been developed. When it is coupled with formation of the pyridinium salt from primary amines, this method enables alkyl amines to be converted to alkyl nitriles. A less toxic cyanide reagent, Zn(CN)2, is utilized, and diverse functional groups and heterocycles are tolerated. The method also enables a one-carbon homologation of alkyl amines via reduction of the nitrile products, in addition to many other potential transformations of the versatile nitrile group.
Visible- And UV-Light-Induced Decarboxylative Radical Reactions of Benzoic Acids Using Organic Photoredox Catalysts
Kubosaki, Suzuka,Takeuchi, Haruka,Iwata, Yutaka,Tanaka, Yosuke,Osaka, Kazuyuki,Yamawaki, Mugen,Morita, Toshio,Yoshimi, Yasuharu
, p. 5362 - 5369 (2020/05/19)
Photoinduced decarboxylative radical reactions of benzoic acids with electron-deficient alkenes, diborane, and acetonitrile under organic photoredox catalysis conditions and mild heating afforded adducts, arylboronate esters, and the reduction product, respectively. The reaction is thought to involve single-electron transfer promoted the generation of aryl radicals via decarboxylation. A diverse range of benzoic acids were found to be suitable substrates for this photoreaction. Only our two-molecule organic photoredox system can work well for the direct photoinduced decarboxylation of benzoic acids.
Titanium(III)-Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non-Free-Radical Mechanism
Weweler, Jens,Younas, Sara L.,Streuff, Jan
supporting information, p. 17700 - 17703 (2019/11/13)
A titanium-catalyzed mono-decyanation of geminal dinitriles is reported. The reaction proceeds under mild conditions, tolerates numerous functional groups, and can be applied to quaternary malononitriles. A corresponding desulfonylation is demonstrated as well. Mechanistic experiments support a catalyst-controlled cleavage without the formation of free radicals, which is in sharp contrast to traditional stoichiometric radical decyanations. The involvement of two TiIII species in the C?C cleavage is proposed, and the beneficial role of added ZnCl2 and 2,4,6-collidine hydrochloride is investigated.
Corresponding amine nitrile and method of manufacturing thereof
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, (2018/05/24)
The present invention relates to a nitrile manufacturing method, which has characteristics of significantly-reduced ammonia source consumption, low environmental pressure, low energy consumption, low production cost, high nitrile purity, high nitrile yield and the like compared with the method in the prior art, wherein nitrile having a complicated structure can be obtained through the method. The present invention further relates to a method for producing a corresponding amine from the nitrile.
Tris(trimethylsilyl)silane-mediated reductive decyanation and cyano transfer reactions of malononitriles
Kawamoto, Takuji,Shimaya, Yudai,Curran, Dennis P.,Kamimura, Akio
supporting information, p. 573 - 575 (2018/04/12)
Reductive decyanation reactions of malononitriles were achieved with tris(trimethylsilyl)silane as a radical mediator. The reaction proceeds via a radical chain mechanism involving a silyl radical addition to the malononitrile to form an imidoyl radical followed by α-cleavage to give a silyl isocyanide and an α-cyano radical. The reaction of a 3-butenyl-substituted malononitrile afforded a decyano/cyanosilylation product in good yield through 1,4-cyano transfer.
A strategy for generating aryl radicals from arylborates through organic photoredox catalysis: Photo-Meerwein type arylation of electron-deficient alkenes
Iwata,Tanaka,Kubosaki,Morita,Yoshimi
supporting information, p. 1257 - 1260 (2018/02/09)
Photoinduced reactions of arylboronic acids with electron deficient alkenes under mild organic photoredox catalysis conditions lead to the formation of Meerwein arylation type adducts via the generation of aryl radicals.
Corresponding amine nitrile and method of manufacturing thereof
-
Paragraph 0132; 0133; 0134; 0136; 0142, (2018/05/24)
The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
Reductive Transformations of Carbonyl Compounds Catalyzed by Rhodium Supported on a Carbon Matrix by using Carbon Monoxide as a Deoxygenative Agent
Yagafarov, Niyaz Z.,Usanov, Dmitry L.,Moskovets, Alexey P.,Kagramanov, Nikolai D.,Maleev, Victor I.,Chusov, Denis
, p. 2590 - 2593 (2015/09/15)
An efficient method for the rhodium on carbon matrix catalyzed preparation of secondary and tertiary amines, cyanoesters, and nitriles through the reductive amination/alkylation of carbonyl compounds was developed, including a convenient procedure for the tandem formal reductive addition of acetonitrile to aldehydes. The catalyst could be reused, and at least three consecutive reaction cycles were performed with comparable efficiency. The method was shown to be compatible with functional groups prone to reduction by hydrogen and complex hydrides. Beyond the matrix: An efficient method for the rhodium on carbon matrix catalyzed preparation of secondary and tertiary amines, cyanoesters, and nitriles through the reductive amination/alkylation of carbonyl compounds is developed, including a convenient procedure for the tandem formal reductive addition of acetonitrile to aldehydes. TON=turnover number.
