120153-68-6Relevant academic research and scientific papers
Synthesis α-Aminonitrile through Anodic Cyanation of N-Benzylpiperidine
Zhao, Ping,Yin, Ying-Wu
, p. 157 - 160 (2004)
Six-membered cyclic α-aminonitrile has been prepared from anodic cyanation of N-benzylpiperidine. Good yields of α-aminonitriles could be obtained through potentiostatic electrolysis under different conditions. The results also explain why high yield α-aminonitriles could not be obtained under constant current electrolysis.
Transition-Metal-Free Reductive Functionalization of Tertiary Carboxamides and Lactams for α-Branched Amine Synthesis
Chiba, Shunsuke,Dixon, Darren J.,Fan, Dongyang,Ong, Derek Yiren
, p. 11903 - 11907 (2020/05/22)
A new method for the synthesis of α-branched amines by reductive functionalization of tertiary carboxamides and lactams is described. The process relies on the efficient and controlled reduction of tertiary amides by a sodium hydride/sodium iodide composite, in situ treatment of the resulting anionic hemiaminal with trimethylsilyl chloride and subsequent coupling with nucleophilic reagents including Grignard reagents and tetrabutylammonium cyanide. The new method exhibits broad functional-group compatibility, operates under transition-metal-free reaction conditions, and is suitable for various synthetic applications on both sub-millimole and on multigram scales.
Iridium-Catalyzed Reductive Strecker Reaction for Late-Stage Amide and Lactam Cyanation
Fuentes de Arriba, ángel L.,Lenci, Elena,Sonawane, Mahendra,Formery, Odilon,Dixon, Darren J.
supporting information, p. 3655 - 3659 (2017/03/21)
A new iridium-catalyzed reductive Strecker reaction for the direct and efficient formation of α-amino nitrile products from a broad range of (hetero)aromatic and aliphatic tertiary amides, and N-alkyl lactams is reported. The protocol exploits the mild and highly chemoselective reduction of the amide and lactam functionalities using IrCl(CO)[P(C6H5)3]2 (Vaska's complex) in the presence of tetramethyldisiloxane, as a reductant, to directly generate hemiaminal species able to undergo substitution by cyanide upon treatment with TMSCN (TMS=trimethylsilyl). The protocol is simple to perform, broad in scope, efficient (up to 99 % yield), and has been successfully applied to the late-stage functionalization of amide- and lactam-containing drugs, and naturally occurring alkaloids, as well as for the selective cyanation of the carbonyl carbon atom linked to the N atom of proline residues within di- and tripeptides.
Redox-neutral α-cyanation of amines
Ma, Longle,Chen, Weijie,Seidel, Daniel
, p. 15305 - 15308 (2012/10/29)
α-Aminonitriles inaccessible by traditional Strecker chemistry are obtained in redox-neutral fashion by direct amine α-cyanation/N-alkylation or alternatively, α-aminonitrile isomerization. These unprecedented transformations are catalyzed by simple carboxylic acids.
The decarboxylative strecker reaction
Das, Deepankar,Richers, Matthew T.,Ma, Longle,Seidel, Daniel
supporting information; experimental part, p. 6584 - 6587 (2012/01/19)
α-Amino acids react with aldehydes in the presence of a cyanide source to form α-amino nitriles in what can be considered a decarboxylative variant of the classical Strecker reaction. This unprecedented transformation does not require the use of a metal catalyst and provides facile access to valuable α-amino nitriles that are inaccessible by traditional Strecker chemistry.
A New and Practical Procedure for the Bruylants Reaction. Zinc-Mediated Synthesis of Tertiary Homoallylamines and β-Aminoesters
Bernardi, Luca,Bonini, Bianca F.,Capitò, Elena,Dessole, Gabriella,Fochi, Mariafrancesca,Comes-Franchini, Mauro,Ricci, Alfredo
, p. 1778 - 1782 (2007/10/03)
N,N-Disubstituted α-aminonitriles undergo Bruylants reaction under Barbier and Reformatsky conditions with activated halides, in the presence of zinc and 10 mol% HOAc. The high yields and the simple operational conditions make this reaction an appealing, approach to N,N-disubstituted homoallylamines and β-aminoesters.
Regio- and Diastereoselective Synthesis of α-Cyanoamines by Anodic Oxidation of 6-Membered α-Silylamines
Gall, Erwan Le,Hurvois, Jean-Pierre,Sinbandhit, Sourisak
, p. 2645 - 2654 (2007/10/03)
The electrochemical cyanation of N-benzyl-substituted cyclic six-membered α-silylamines including tetrahydroquinoline and piperidine derivatives was studied. The results of these investigations demonstrate that α-silylamines are valuable precursors for the preparation of the corresponding α-cyanoamines. The TMS group α to the N atom not only governs the chemoselectivity of the iminium formation through a preferential desilylation reaction under the experimental conditions (i.e., amine cation radical desilylation versus deprotonation), it also lowers the oxidation potential of tertiary amines compared to their non-TMS counterparts. Both the stereoselectivity and regioselectivity of the cyanide addition were investigated with 3-methylpiperidine as the model compound. The formation of a single cis diastereoisomer in which the 2-cyano group is axial and the 5-methyl group is equatorial, indicates that the addition of the cyanide anion onto the iminium species is under stereoelectronic control. In addition, the redox reaction, involving the intermediate nitrogen-centered cation radical and the cyanide anions played no role, because the α-silyl radical has such a short lifetime.
Synthesis of β-Amino Esters Using the Reformatsky Reaction with α-Amino Nitriles
Dartiguelongue, Caroline,Payan, Steve,Duval, Olivier,Gomes, Luis M.,Waigh, Roger D.
, p. 769 - 772 (2007/10/03)
The chemical behavior of α-amino nitriles towards the Reformatsky reagent has been studied.Under certain conditions, secondary aliphatic α-amino nitrile derivatives yielded a mixture of four products consisting of a β-amino ester, a β-lactam, a bulky tert
Application of Electro-Oxidative α-Cyanation of Aza-Rings to the Synthesis of Gephyrotoxin 223AB
Yang, Teng-Kuei,Yeh, Shun-Tsai,Lay, Yen-Yuan
, p. 1711 - 1716 (2007/10/02)
Six and five-membered cyclic α-cyanoamines have been prepared efficiently from N-benzylpiperidine and N-benzylpyrrolidine.These α-cyanoamines were successfully used in the synthesis of gephyrotoxin 223AB.
