Recent advances and perspectives in ruthenium-catalyzed cyanation reactions

• Thaipparambil Aneeja,
• Cheriya Mukkolakkal Abdulla Afsina,
• Padinjare Veetil Saranya and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 37–52, doi:10.3762/bjoc.18.4

• the oxidative cyanation reaction [30]. The prepared catalyst was found highly active in the oxidative cyanation of tertiary amines to the corresponding α-aminonitriles in excellent yields. The cyanation reaction of N,N-dimethylaniline using NaCN catalyzed by ruthenium-carbamato complex in AcOH/MeOH

• the electron-withdrawing ones. The N-aryl cyclic amines including N-phenylpiperidine, N-phenyltetrahydroisoquinoline, and N-phenylpyrrolidine smoothly reacted to deliver the required α-aminonitriles in good yields. Under the optimized conditions, aliphatic tributylamine failed to achieve the desired

• trimethylsilyl cyanide (TMSCN) in acetonitrile solvent under CFL light irradiation. 4 Miscellaneous An efficient methodology for the synthesis of α-aminonitriles via the one-pot coupling of aldehydes, amines and trimethylsilyl cyanide was reported [46]. This reaction was catalyzed by RuCl3 and used acetonitrile

Ultrasound-assisted Strecker synthesis of novel 2-(hetero)aryl-2-(arylamino)acetonitrile derivatives

• Emese Gal,
• Luiza Gaina,
• Hermina Petkes,
• Alexandra Pop,
• Castelia Cristea,
• Gabriel Barta,
• Dan Cristian Vodnar and
• Luminiţa Silaghi-Dumitrescu

Beilstein J. Org. Chem. 2020, 16, 2929–2936, doi:10.3762/bjoc.16.242

• -benzoxazole [13] or different other acetohydrazines [14], complexation of phenothiazinyl-chalcone using diiron nonacarbonyl [15], and regioselective oxidation [16]. α-Aminonitriles are versatile synthetic intermediates that are readily obtainable by a Strecker reaction involving the addition of a cyanide

Recent applications of porphyrins as photocatalysts in organic synthesis: batch and continuous flow approaches

• Rodrigo Costa e Silva,
• Luely Oliveira da Silva,
• Aloisio de Andrade Bartolomeu,
• Timothy John Brocksom and
• Kleber Thiago de Oliveira

Beilstein J. Org. Chem. 2020, 16, 917–955, doi:10.3762/bjoc.16.83

• /secondary amine oxidation under continuous-flow conditions using TPP as photocatalyst for singlet oxygen generation, and subsequently, the product imines were trapped with trimethylsilyl cyanide (TMSCN) for producing the α-aminonitriles (Scheme 56) [105]. A library of α-aminonitriles was produced by this

• using 4 mol % of tetra-n-butylammonium fluoride (TBAF) as an activator of TMSCN (conditions B). Following this second protocol, the primary α-aminonitriles were rapidly prepared in relevant yields (up to 87%) and converted to the corresponding α-amino acids by hydrolysis of the nitrile (Scheme 57

• ]. Che and co-workers showed that a variety of nucleophiles can be used for the α-functionalization of N-aryltetrahydroisoquinolines using a low Pd-TPFPP loading. This photocatalyst provided the α-aminonitriles in 71–85%, β-nitroamines in 72–83%, β-diester amines in 68–74%, and α-amino phosphonates in 63

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• -donating and -withdrawing substitutions on benzaldehydes or in benzoic acids have worked well under the mechano-chemical conditions [116]. In a multicomponent Strecker reaction the syntheses of α-aminonitriles are generally done by condensation of aldehydes, ammonia and hydrogen cyanide [117][118]. The

• aminonitriles are important synthons for the preparation of nitrogen-containing heterocycles and amino acids [119]. In 2016, Bolm and co-workers reported a mechanochemical synthesis of α-aminonitriles using benzaldehyde, benzyl amine, KCN and the milling auxiliary SiO2 to isolate 70–97% of α-aminonitriles as

• reaction of electron-rich arenes [88][98]. Mechanochemical aryl halogenation reaction using trihaloisocyanuric acids [100]. Mechanochemical fluorination reaction by LAG method [102]. Mechanochemical Ugi reaction [116]. Mechanochemical Passerine reaction [116]. Mechanochemical synthesis of α-aminonitriles

The reductive decyanation reaction: an overview and recent developments

• Jean-Marc R. Mattalia

Beilstein J. Org. Chem. 2017, 13, 267–284, doi:10.3762/bjoc.13.30

• ether cleavage. Aluminium- and borohydrides and the use of sodium hydride Reduction of α-aminonitriles Bifunctional α-aminonitriles exhibit several modes of reactivity. Recent reviews demonstrated the richness of this chemistry and emphasized synthetic applications particularly in heterocyclic chemistry

• [41][42][43][44]. The reductive decyanation of α-aminonitriles under metal dissolving conditions is a common procedure that proceeds through a two-electron-transfer pathway (Scheme 1) [23][44]. In the ionic pathway, the loss of the cyanide ion yields an iminium cation that can be reduced by various

• borohydrides for substrates other than α-aminonitriles has been described for more specific cases and usually displays moderate yields [76][77][78][79]. Recently, the DIBAL-H-induced decyanation of gem-dicyanodihydroazulene derivatives was described but only poor yields were reported [80]. Chiba et al

Proton transfers in the Strecker reaction revealed by DFT calculations

• Shinichi Yamabe,
• Guixiang Zeng,
• Wei Guan and
• Shigeyoshi Sakaki

Beilstein J. Org. Chem. 2014, 10, 1765–1774, doi:10.3762/bjoc.10.184

• alanine in the acidic solution. The traditional Strecker reaction gave racemic α-aminonitriles (mixtures of equal amounts of R and S forms), where an imine RCH=NH was considered to be the key intermediate [2]. Three typical reactions are presented in Scheme 1(b) [3]. In 1963, Harada reported the first

• cyclic dipeptide [5]. In these reactions, N-substituted imines react with HCN to yield (S)-α-aminonitriles with remarkably high enantiomeric excess (ee). One example is shown in Scheme 3. However, when benzaldehyde and NH3 instead of the N-substituted imine were employed as the substrates, the reaction

• reaction have not been elucidated. As shown in Scheme 1, the Strecker reaction includes two reaction stages. The first reaction stage is the condensation of aldehydes with ammonia and hydrogen cyanide leading to α-aminonitriles . The second reaction stage is the hydrolysis of the nitrile group. In these

Simple two-step synthesis of 2,4-disubstituted pyrroles and 3,5-disubstituted pyrrole-2-carbonitriles from enones

• Murat Kucukdisli,
• Dorota Ferenc,
• Marcel Heinz,
• Christine Wiebe and
• Till Opatz

Beilstein J. Org. Chem. 2014, 10, 466–470, doi:10.3762/bjoc.10.44

• -carbonitriles. Keywords: α-aminonitriles; cyclization; heterocycles; microwave-assisted synthesis; pyrroles; Introduction Heterocycles are the largest class of organic compounds [1]. Among them, pyrroles have a distinguished position in the chemistry of living organisms due to their close biogenetic

Multicomponent reactions II

• Thomas J. J. Müller

Beilstein J. Org. Chem. 2014, 10, 115–116, doi:10.3762/bjoc.10.7

• been around in organic chemistry since the very early days. Indeed, the first example known in literature, the Strecker synthesis of α-aminonitriles [2], has been developed into an industrial process for the production of methionine in an annual scale of several hundreds of thousand tons per year. In

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• aminoacetal formation. The chiral auxilliary can be removed by further treatment with DIBAL-H and Pb(OAc)4 (Scheme 9) [8]. The Strecker reaction, employing aldehydes or ketones and a cyanide source, is a very useful route for the preparation of α-aminonitriles 19 or 20. A general and efficient three-component

An overview of the key routes to the best selling 5-membered ring heterocyclic pharmaceuticals

• Marcus Baumann,
• Ian R. Baxendale,
• Steven V. Ley and
• Nikzad Nikbin

Beilstein J. Org. Chem. 2011, 7, 442–495, doi:10.3762/bjoc.7.57

• good yield (Scheme 34) [51]. More recently, Zhong and co-workers [52] reported a highly efficient one-pot procedure starting from N-acylated α-aminonitriles 173. The desired 2,4,5-trisubstituted imidazole core 178 is formed in high yield in the presence of carbon tetrachloride and triphenylphosphine

Cobalt(II) chloride catalyzed one-pot synthesis of α-aminonitriles

• Surya K. De

Beilstein J. Org. Chem. 2005, 1, No. 8, doi:10.1186/1860-5397-1-8

• Surya K. De Department of Medicinal Chemistry and Molecular Pharmacology, School of Pharmacy and Purdue Cancer Center, Purdue University, West Lafayette, IN 47907, USA 10.1186/1860-5397-1-8 Abstract A simple and efficient method has been developed for the synthesis of α-aminonitriles by a one-pot

• α-aminonitriles, which are useful intermediates for the synthesis of amino acids and nitrogen-containing heterocycles such as thiadiazoles, imidazoles, etc [2][3]. They are usually prepared by the nucleophilic addition of cyanide anion to imines. Numerous methods describing the preparation of α

• synthesis of α-aminonitriles. In continuation of our work to develop new organic transformations, [11][12][13][14][15][16][17] I report herein that cobalt(II) chloride which acts as a mild Lewis acid might be a useful and inexpensive catalyst for the synthesis α-aminonitrile. Although cobalt(II) chloride