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.
Off-Equilibrium Speed Control of a Multistage Molecular Rotor: 2-Fold Chemical Fueling by Acid or Silver(I)
Goswami, Abir,Saha, Suchismita,Elramadi, Emad,Ghosh, Amit,Schmittel, Michael
, p. 14926 - 14935 (2021/09/18)
Driving conformational motion in defined off-equilibrium oscillations can be achieved using chemical fuels. When the ultrafast turnstile 1 (k298> 1012Hz) was fueled with 2-cyano-2-phenylpropanoic acid ( Fuel 1 ), the diprotonated rotor [H2( 1 )]2+(k298= 84.0 kHz) formed as a transient regaining the dynamics of the initial turnstile after consumption of the fuel (135 min). Upon addition of silver(I) ( Fuel 2 ) to turnstile 1 , the metastable rotor [Ag2( 1 )]2+(k298= 1.57 Hz) was initially furnished, but due to a consequentially triggered SN2 reaction, the Ag+ions were consumed as insoluble AgBr along with regeneration of 1 (within 3 h). The off-equilibrium fast ? slow rotor conversions fueled by acid and silver(I) were directly monitored by fluorescence and1H NMR. In addition, metal ion exchange was fueled enabling off-equilibrium oscillations between rotors [Li2( 1 )]2+? [Ag2( 1 )]2+. In the end, both sustainability and efficiency of the process were increased in unison by using the interfering proton waste in the formation of a [2]pseudorotaxane.
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.
