Cyanation Of Amines Research Articles

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.

Chiral Piperidines from Acyclic Amines Via Enantioselective, Radical-Mediated δ C-H Cyanation

Piperidines are the most prevalent heterocyclic core found in medicines. Yet, while these structures often contain chiral substituents, there are no robust methods for the synthesis of enantioenriched, substituted piperidines. Current approaches rely on the reduction of pyridines or C-H functionalizations to afford racemic mixtures that must then be resolved. To solve this challenge, we proposed an adaptation of the century-old Hofmann-Loffler-Freytag (HLF) reaction may afford this privileged heterocycle. This approach would require interruption of the regioselective δ C-H amination of acyclic amines to instead incorporate a carbonyl equivalent at the δ position. Moreover, this C-C bond would need to be installed with high stereoselectivity (>90% enantiomeric excess) for the first time. To this end, a catalytic method for remote, enantioselective C-C formation has been developed. This δ C-H cyanation of amines is enabled by a chiral Cu catalyst, which both initiates and terminates an intramolecular hydrogen atom transfer (HAT) mechanism. The broad scope and utility of this catalytic method for enantioselective δ C-C formation by an N-centered radical relay is presented, as well as the conversion of the resulting enantioenriched d amino nitriles to a family of chiral piperidines. Experiments probing the chemo-, regio-, and enantio-selectivity of this HAT mechanism are also included to enable extension to other δ C-H functionalizations in a stereoselective fashion.

Magnetic graphitic carbon nitride: its application in the C-H activation of amines.

Magnetic graphitic carbon nitride, Fe@g-C3N4, has been synthesized by adorning a graphitic carbon nitride (g-C3N4) support with iron oxide via non-covalent interaction. The magnetically recyclable catalyst showed excellent reactivity for the expeditious C-H activation and cyanation of amines.

ChemInform Abstract: The Cyanamide Moiety: Synthesis and Reactivity

AbstractReview: ca. 120 refs.

The Cyanamide Moiety, Synthesis and Reactivity

The cyanamide moiety provides many opportunities as a building block for the synthesis of nitrogen-containing heterocycles. This review discusses the reported methods for the preparation of alkyl- and N-acylcyanamides and illustrates their reactivity vis-a-vis nucleophilic additions, cycloadditions, radical chemistry and coordination chemistry. 1 Introduction 2 Biological Relevance of the Cyanamide Moiety 3 Access to Cyanamides 3.1 Cyanation of Amines 3.2 Palladium Catalysis 3.3 Deoxygenation of Isocyanates 3.4 Desulfurization of Thioureas 4 Reactivity of Cyanamides 4.1 Nucleophilic Additions 4.2 Cycloadditions 4.3 Additions to Carbonyl Groups 4.4 Chlorinations and Oxidations with tert-Butyl-N-chloro­cyanamide 4.5 Cyanamides as Radical Partners 5 Coordination Chemistry of Cyanamides 6 Conclusion

Oxidative Cyanation of Amines Using Heterogeneous Iron Phthalocyanines

Oxidative Cyanation of Amines Using Heterogeneous Iron Phthalocyanines<b />

Electroorganic chemistry 139. Electroreductive decyanation of nitriles and its application to synthesis of α-alkylamines

Electroreduction of nitriles gave the corresponding decyanated products when Zn was used as the material of cathode in aprotic solvent (DMF or MeCN) containing Et 4NOTs as a supporting electrolyte. Alkylation of amines at the α-position was effectively achieved by cyanation of amines at the α-position, and α-alkylation of the resultant α-amino nitriles followed by the electroreductive decyanation.