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.
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.
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.