1823-91-2Relevant articles and documents
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].
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
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
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Baldinger,Nieuwland
, p. 2851 (1933)
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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.
Base-controlled chemoselectivity: direct coupling of alcohols and acetonitriles to synthesise α-alkylated arylacetonitriles or acetamides
Bai, Liang,Ge, Min-Tong,Li, Chen,Qiu, Yuan-Rui,Wang, Ying,Xia, Ai-Bao,Xu, Dan-Qian
supporting information, p. 15200 - 15204 (2021/09/06)
We achieved chemoselective synthesis of α-alkylated arylacetonitriles and acetamides by combining Ir complex-catalysed direct coupling of alcohols and nitriles by a simple adjustment of the base. Methanol and ethanol performed well as the alkylating reagents. This method of acetonitrile alkylation provided a novel approach for carbon chain extension.
Metal-Free Deoxygenation of Chiral Nitroalkanes: An Easy Entry to α-Substituted Enantiomerically Enriched Nitriles
Pirola, Margherita,Faverio, Chiara,Orlandi, Manuel,Benaglia, Maurizio
, p. 10247 - 10250 (2021/06/18)
A metal-free, mild and chemodivergent transformation involving nitroalkanes has been developed. Under optimized reaction conditions, in the presence of trichlorosilane and a tertiary amine, aliphatic nitroalkanes were selectively converted into amines or nitriles. Furthermore, when chiral β-substituted nitro compounds were reacted, the stereochemical integrity of the stereocenter was maintained and α-functionalized nitriles were obtained with no loss of enantiomeric excess. The methodology was successfully applied to the synthesis of chiral β-cyano esters, α-aryl alkylnitriles, and TBS-protected cyanohydrins, including direct precursors of four active pharmaceutical ingredients (ibuprofen, tembamide, aegeline and denopamine).