15429-22-8

Upstream product

• 7677-24-9 trimethylsilyl cyanide 
• 100-52-7 benzaldehyde 
• 103-49-1 dibenzylamine 
• 620-40-6 tribenzylamine 
• 773837-37-9 sodium cyanide 
• 90540-43-5 Dibenzyl-[(tert-butyl-dimethyl-silanyloxy)-phenyl-methyl]-amine 
• 143-33-9 sodium cyanide 

Relevant academic research and scientific papers

Photoredox-Catalyzed Cα-H Cyanation of Unactivated Secondary and Tertiary Aliphatic Amines: Late-Stage Functionalization and Mechanistic Studies

This paper describes the development and mechanistic studies of a general, high-yielding amine Cα-H cyanation protocol via photoredox catalysis. Inexpensive NaCN is employed as the cyanide source and air is the external oxidant, resulting in mild and highly functional group tolerant conditions. Notably, efficient Cα-H cyanations of secondary and tertiary aliphatic amines and of complex, biologically active compounds (drugs) can be performed using the established methodology. Mechanistic studies suggest that the carboxylic acid additive has three effects: formation of a stabilizing hemiaminal intermediate, prevention of catalyst decomposition by protonating the substrate, and modulation of fluorescence quenching of the photoexcited catalyst species.

Iron-Catalyzed α-C-H Cyanation of Simple and Complex Tertiary Amines

This manuscript details the development of a general and mild protocol for the α-C-H cyanation of tertiary amines and its application in late-stage functionalization. Suitable substrates include tertiary aliphatic, benzylic, and aniline-type substrates and complex substrates. Functional groups tolerated under the reaction conditions include various heterocycles and ketones, amides, olefins, and alkynes. This broad substrate scope is remarkable, as comparable reaction protocols for α-C-H cyanation frequently occur via free radical mechanisms and are thus fundamentally limited in their functional group tolerance. In contrast, the presented catalyst system tolerates functional groups that typically react with free radicals, suggesting an alternative reaction pathway. All components of the described catalyst system are readily available, allowing implementation of the presented methodology without the need for lengthy catalyst synthesis.

Nano cobalt-copper ferrite catalyzed regioselective α-C(sp3)–H cyanation of amines: Secondary, tertiary, and drug molecules

Oxidative cyanation of sp3C–H bonds at the α position of amines was achieved using CoCuFe2O4 as a catalyst and NaCN as an inexpensive cyanide source at room temperature. CoCuFe2O4 was found to be an active catalyst for Csp [3]-Csp coupling, efficiently delivering valuable α-aminonitriles from tertiary/secondary amines in good yields. The corresponding products were obtained with high selectivity toward α position. In addition, functional group tolerance offered the opportunity for application in late-stage functionalization of biologically active molecules. This transformation proceeds convenient on a gram-scale, and the catalyst can be reused for several runs with consistent catalytic activity.

Iron-catalyzed generation of α-amino nitriles from tertiary amines

The use of iron(II) chloride as catalyst, trimethylsilyl cyanide as source of cyanide ions, and tert-butyl hydroperoxide as oxidant enabled the conversion of aromatic, benzylic, and aliphatic tertiary amines into α-Amino nitriles under mild conditions. Chemoselective functionalization of N-CH3 to N-CH2CN was achieved in the presence of Nbenzyl and N-alkyl groups. N,N-Dialkylanilines, PhNR2, with R=Et, Bu, Bn furnished the alkyl-(aryl)aminoacetonitriles PhN(R)CH2CN as the main products accompanied by α-Amino nitriles generated by ordinary a-cyanation of the aniline PhNR2. Formation of PhN(R)CH2CN was rationalized by oxidative degradation of N,N-dialkylanilines to N-alkylanilines, their condensation with formaldehyde, generated by oxidation of the solvent methanol, and final trapping of the thus formed iminium ions by cyanide.

Synthesis of α-amino nitriles through Strecker-type reaction using SO3H -functionalized ionic liquid as a homogeneous and water tolerant-acidic catalyst

Task-specific ionic liquid (TSIL) bearing a sulfonic acid group in imidazolium cation (10 mol %), was found to be an effective catalyst for a Strecker-type reaction in water at room temperature. A wide variety of aldehydes/ketones, amines and TMSCN as cya

Tropylium ion mediated α-cyanation of amines

Tropylium ion mediated α-cyanation of amines is described. Even in the presence of KCN, tropylium ion is capable of oxidizing various amine substrates, and the resulting iminium ions undergo salt metathesis with cyanide ion to produce aminonitriles. The byproducts of this transformation are simply cycloheptatriene, a volatile hydrocarbon, and water-soluble potassium tetrafluoroborate. Thirteen total substrates are shown for the α-cyanation procedure, including a gram scale synthesis of 17β-cyanosparteine. In addition, a tropylium ion mediated oxidative aza-Cope rearrangement is demonstrated.

Oxalic acid as a simple and efficient organocatalyst for three-component synthesis of α-amino nitriles

A simple, efficient, and general method has been developed for the synthesis of α-amino nitriles. Oxalic acid as a Br?nsted acid promotes the addition of TMSCN to various imines (generated in situ).

Trifluoroethanol as a metal-free, homogeneous and recyclable medium for the efficient one-pot synthesis of α-amino nitriles and α-amino phosphonates

Trifluoroethanol is found to be an efficient and recyclable medium in promoting one-pot, three-component coupling reactions of aldehydes or ketones, amines and trimethylsilyl cyanide or trimethyl phosphite to afford the corresponding α-amino nitriles or α-amino phosphonates in high yields. This protocol does not require the use of an acid or base catalyst.

Sulfamic acid: an efficient, cost-effective and recyclable solid acid catalyst for the three-component synthesis of α-amino nitriles

α-Amino nitriles are synthesized by the three-component coupling reaction of aldehydes, amines and trimethylsilyl cyanide using sulfamic acid as a heterogeneous solid acid catalyst, under solvent-free conditions in excellent yields. The catalyst was recov

Solvent-free synthesis of racemic α-aminonitriles

A very simple one-step, environmentally friendly procedure for the synthesis of α-aminonitriles from aldehydes and ketones, using trimethylsilyl cyanide in the absence of solvent, is reported. The active catalyst of this three-component (Strecker) reaction was the amine employed in the transformation. In general, aldehydes react more rapidly than ketones and give almost quantitative yields of the corresponding α-aminonitriles in less than fifteen minutes. However, only cyclic ketones afford the corresponding α-aminonitriles in excellent chemical yields under these conditions. Georg Thieme Verlag Stuttgart.