15190-05-3Relevant academic research and scientific papers
One-Pot Synthesis of α-Amino Nitrile Units through Alkylative Strecker Cyanation from Formamides
Yu, Bao,Bodinier, Florent,Saague-Tenefo, Maximiliene,Gerardo, Patrice,Ardisson, Janick,Lannou, Marie-Isabelle,Sorin, Geoffroy
, p. 3634 - 3640 (2021/07/22)
In this work, we describe the one-pot synthesis of α-amino nitrile units by the concomitant addition of alkyl (or aryl) Grignard reagents and TMS cyanide through alkylative Strecker cyanation from readily available formamides. The reaction is broad in sco
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
supporting information, 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.
Orthoamides, XXXIII.-Contributions to the Chemistry of Bis(dialkylamino)acetonitriles
Kantlehner, Willi,Baur, Richard,Bredereck, Hellmut
, p. 358 - 371 (2007/10/02)
Bis(dialkylamino)acetonitriles 2a-d react with acetyl chloride and antimony pentachloride to give N,N,N',N'-tetraalkylformamidinium hexachloroantimonates 5a-d.Reaction of p-nitrophenol with 2a,b affords N,N,N',N'-tetraalkylformamidinium salts 8a,b, while reaction of aromatic aldehydes 11 with compounds 2 gives aryl(dialkylamino)acetonitriles 12.Phenyl isothiocyanate reacts with the nitriles 2a-c to give 1:1 adducts for which the structure of N,N,N',N'-tetraalkylformamidinium cyano-N-(phenyl)thioformamidates 19 is proposed.N,N,N',N'-Tetraalkylformamidinium p-toluenesulfonates 30a,b have been prepared from nitriles 2a,b and methyl p-toluoenesulfonate (28).Alkylation of 2c with 28 at higher temperatures affords 1,1-dimethylpiperidinium p-toluoenesulfonate (34) and a small amount (1-piperidinyl)malonodinitrile (33).The nitrile 2a reacts with CH acidic compounds such as ethyl cyanoacetate, malonodinitrile and benzyl cyanide to form the enamines 38.
