Ultrasound-promoted organocatalytic enamine–azide [3 + 2] cycloaddition reactions for the synthesis of ((arylselanyl)phenyl-1H-1,2,3-triazol-4-yl)ketones

• Gabriel P. Costa,
• Natália Seus,
• Juliano A. Roehrs,
• Raquel G. Jacob,
• Ricardo F. Schumacher,
• Thiago Barcellos,
• Rafael Luque and
• Diego Alves

Beilstein J. Org. Chem. 2017, 13, 694–702, doi:10.3762/bjoc.13.68

• independently using as substrates ethyl acetoacetate (2f), ethyl benzoylacetate (2g), 3-oxo-N-phenylbutanamide (2h), 3-oxo-N-(p-tolyl)butanamide (2i), benzoylacetonitrile (2j) and 4-toluoylacetonitrile (2k). The corresponding esters 3k,l [33], amides 3m,n [34] and nitriles 3o,p [36] were obtained in good yields

Isoxazole derivatives as new nitric oxide elicitors in plants

• Anca Oancea,
• Emilian Georgescu,
• Florentina Georgescu,
• Alina Nicolescu,
• Elena Iulia Oprita,
• Catalina Tudora,
• Lucian Vladulescu,
• Marius-Constantin Vladulescu,
• Florin Oancea and
• Calin Deleanu

Beilstein J. Org. Chem. 2017, 13, 659–664, doi:10.3762/bjoc.13.65

• synthetic approaches towards the isoxazole core include the reactions of hydroxylamine with aryl-β-diketones [20], α,β-unsaturated carbonyl compounds [21], or α,β-unsaturated nitriles [22], and 1,3-dipolar cycloaddition reactions between alkenes or alkynes and nitrile oxides [23][24][25]. Nitrile oxides are

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• methyl trifluoromethanesulfonate, in dichloromethane or 1,2-dichloroethane in high yields (Scheme 54). 1.5 From nitriles Nitrile derivatives are also useful substrates for the synthesis of 1-indanones. An efficient synthesis of 1-indanones 194 via palladium-catalyzed cyclization of 3-(2-iodoaryl

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

• removal of the cyano group from cyclic substrates [8], in 2006 we published a review reporting various methods allowing the reductive decyanation reaction that transforms organic nitriles into the parent alkane [9]. Even if chemical procedures previously described are still of relevance in organic

• proton source (Scheme 1). Using Na/NH3 or Li/EtNH2 solutions, Arapakos obtained the best yields for the decyanation of phenyl-substituted acetonitriles, tertiary alkyl, and aromatic nitriles. However, primary and secondary nitriles also led to the reduction to the amine [10][16]. This drawback can be

• . Rojas et al. proposed a convenient two-step pathway for the preparation of alkyl α,ω-dienes 3. These dienes are well-known precursors in ring-closing metathesis (RCM) and acyclic diene metathesis (ADMET) chemistry [32]. They first reported the quantitative α-alkylation of primary nitriles 1 [33]. In a

Continuous-flow synthesis of highly functionalized imidazo-oxadiazoles facilitated by microfluidic extraction

• Ananda Herath and
• Nicholas D. P. Cosford

Beilstein J. Org. Chem. 2017, 13, 239–246, doi:10.3762/bjoc.13.26

• point solvent removal step. Conclusion In summary, we have developed a telescoped continuous-flow method for the synthesis of diversely substituted imidazo[1,2-a]pyridine-2-yl-1,2,4-oxadiazole derivatives directly from commercial nitriles, aminopyridine carboxylic acids and hydroxylamine. Moreover, we

Iodination of carbohydrate-derived 1,2-oxazines to enantiopure 5-iodo-3,6-dihydro-2H-1,2-oxazines and subsequent palladium-catalyzed cross-coupling reactions

• Michal Medvecký,
• Igor Linder,
• Luise Schefzig,
• Hans-Ulrich Reissig and
• Reinhold Zimmer

Beilstein J. Org. Chem. 2016, 12, 2898–2905, doi:10.3762/bjoc.12.289

• triflates [46][47] or alkenyl halides [48][49] forming α,β-unsaturated nitriles. As shown in Scheme 7, we adopted a protocol described by Yamamura and Murahashi [48] and found that the palladium-catalyzed coupling of anti-4d with potassium cyanide in the presence of 18-crown-6 at 80 °C in toluene afforded

Robust C–C bonded porous networks with chemically designed functionalities for improved CO₂ capture from flue gas

• Damien Thirion,
• Joo S. Lee,
• Ercan Özdemir and
• Cafer T. Yavuz

Beilstein J. Org. Chem. 2016, 12, 2274–2279, doi:10.3762/bjoc.12.220

• ]. HCPs are mainly synthesized through Friedel–Crafts alkylation using iron chloride and thus, are not relying on precious metals. Unfortunately, Friedel–Crafts reactions are not very tolerant to functional groups like nitriles or amines [7]. On the other hand, structures incorporating heteroatoms, such

• Knoevenagel condensation of benzyl nitriles and aldehydes produces C–C bonded products with labile nitrile functionalities. In fact, nitrile groups have been shown in porous polymers (particularly in polymers of intrinsic microporosity (PIMs)) to be good precursors to several functionalities like carboxylic

• highly porous cyanovinylene networks could be obtained through Knoevenagel condensation of benzylic nitriles and aldehydes by choosing appropriate building blocks. The resulting nitrile functionalities in COP-156 could be easily modified into free amine or amidoxime groups. The amine functionalities in

Elongated and substituted triazine-based tricarboxylic acid linkers for MOFs

• Arne Klinkebiel,
• Ole Beyer,
• Barbara Malawko and
• Ulrich Lüning

Beilstein J. Org. Chem. 2016, 12, 2267–2273, doi:10.3762/bjoc.12.219

• trimerization of respective nitriles [13]. Unsymmetric 1,3,5-triazines 3 can be made by combining one equivalent of an acid chloride with two equivalents of a nitrile [14][15][16] (for a recently described alternative access to unsymmetrical 1,3,5-triazines; see [17]). In the presence of a suitable Lewis acid

• such as antimony(V) chloride, the acid chloride condenses with the nitriles to form an oxadiazinium salt from which the triazine can be obtained by reaction with ammonia (Figure 4). The respective syntheses have successfully been carried out with nitro and methoxy-substituted benzoyl chlorides 5b and

Diastereoselective synthesis of 3,4-dihydro-2H-pyran-4-carboxamides through an unusual regiospecific quasi-hydrolysis of a cyano group

• Mikhail Yu. Ievlev,
• Oleg V. Ershov,
• Mikhail Yu. Belikov,
• Angelina G. Milovidova,
• Viktor A. Tafeenko and
• Oleg E. Nasakin

Beilstein J. Org. Chem. 2016, 12, 2093–2098, doi:10.3762/bjoc.12.198

• TCNE and ketones) with aldehydes in an acidic media. An unusual process of quasi hydrolysis of the cyano group was observed in the course of the described regio- and diastereoselective transformation. Keywords: diastereoselectivity; 3,4-dihydro-2H-pyran-4-carboxamide; nitriles; pyran; quasi-hydrolysis

Microwave-assisted cyclizations promoted by polyphosphoric acid esters: a general method for 1-aryl-2-iminoazacycloalkanes

• Jimena E. Díaz,
• María C. Mollo and
• Liliana R. Orelli

Beilstein J. Org. Chem. 2016, 12, 2026–2031, doi:10.3762/bjoc.12.190

• acid type. They have been widely used for several synthetically useful transformations like dehydration of amides leading to nitriles [23][24] or the Beckmann rearrangement [23][25]. They have also been employed in the synthesis of heterocycles such as benzimidazoles, benzothiazoles, benzoxazoles [23

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

• Maurizio Selva,
• Alvise Perosa,
• Sandro Guidi and
• Lisa Cattelan

Beilstein J. Org. Chem. 2016, 12, 1911–1924, doi:10.3762/bjoc.12.181

• reported results for the synthesis of esters from the reaction of nitriles and alcohols [48]. 4-(3-Methyl-1-imidazolium)-1-butanesulfonic acid triflate ([HSO3-BMIM][CF3SO3]) has been chosen as a model organocatalyst to explore the kinetics of the transesterification of methyl acetate with ethanol [49][50

Synthesis and properties of fluorescent 4′-azulenyl-functionalized 2,2′:6′,2″-terpyridines

• Adrian E. Ion,
• Liliana Cristian,
• Mariana Voicescu,
• Masroor Bangesh,
• Augustin M. Madalan,
• Daniela Bala,
• Constantin Mihailciuc and
• Simona Nica

Beilstein J. Org. Chem. 2016, 12, 1812–1825, doi:10.3762/bjoc.12.171

• development of an efficient ruthenium catalyst for selective oxidation of both aliphatic and aromatic amines to nitriles [22]. The catalytic effectiveness of this ruthenium terpyridine complex was ascribed to the polarization effect of the azulene moiety attached at the terpyridine unit and it was sustained

One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

• Roman Yu. Peshkov,
• Elena V. Panteleeva,
• Wang Chunyan,
• Evgeny V. Tretyakov and
• Vitalij D. Shteingarts

Beilstein J. Org. Chem. 2016, 12, 1577–1584, doi:10.3762/bjoc.12.153

• -dienecarbonitriles 8, and alkylbenzenes 9 (together, up to 25%). According to the total reaction scheme, these byproducts arise via alkylation of the anionic forms of nitriles 1 and 2 [26]. The latter appear in the reaction media due to the electron transfer from 12− to neutral cyanoarene 2 (Scheme 2). Of note, 4,4

• nitriles containing substituents of different natures and positions were used in the reaction (Table 2). We chose the nitriles that had earlier effectively underwent a cross-coupling with dianion 12− [24][25], in particular, 2- and 3-methyl (2b,c), 2- and 3-methoxy- (2d,e), and 2-fluorobenzonitrile (2f

Synthesis of 2-substituted tetraphenylenes via transition-metal-catalyzed derivatization of tetraphenylene

• Shulei Pan,
• Hang Jiang,
• Yanghui Zhang,
• Yu Zhang and
• Dushen Chen

Beilstein J. Org. Chem. 2016, 12, 1302–1308, doi:10.3762/bjoc.12.122

• into other functionalities [58][59]. The Larock group reported a novel Pd-catalyzed addition of nitriles to an arene C–H bond for the synthesis of aryl ketones [60][61]. Following the Larock’s conditions, we investigated the carbonylation of tetraphenylene (1) and the carbonylated product 5a was

• nitriles 4b–k including aromatic and aliphatic ones, were reacted with tetraphenylene (1) to give the corresponding carbonyl products 5b–k (Scheme 1). Both substrates containing either an electron-donating methyl group or electron-withdrawing trifluoromethyl group were suitable for the reaction. In

• addition, halogen-substituted nitriles, including F, Cl, and Br substituents, were well-tolerated under the standard reaction conditions. Also, methyl 4-cyanobenzoate and 1-naphthonitrile were successfully reacted with tetraphenylene to form the corresponding carbonylated products. It is worth mentioning

Conjugate addition–enantioselective protonation reactions

• James P. Phelan and
• Jonathan A. Ellman

Beilstein J. Org. Chem. 2016, 12, 1203–1228, doi:10.3762/bjoc.12.116

• –enantioselective protonation using α,β-unsaturated nitriles has remained unexplored for substrates other than methacrylonitrile. The Togni lab has explored using ferrocenyl tridentate nickel(II) and palladium(II) complexes as chiral Lewis acid catalysts for the hydrophosphination and hydroamination of

Synthesis of highly functionalized 2,2'-bipyridines by cyclocondensation of β-ketoenamides – scope and limitations

• Paul Hommes and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2016, 12, 1170–1177, doi:10.3762/bjoc.12.112

• led to undesired side reactions, e.g., deacylation or oligomerization processes. The development of the discussed pyridine syntheses by cyclocondensation reactions of β-ketoenamides was inspired by a serendipitously discovered three-component reaction of lithiated alkoxyallenes, nitriles and

Synthesis of 2-oxindoles via 'transition-metal-free' intramolecular dehydrogenative coupling (IDC) of sp² C–H and sp³ C–H bonds

• Nivesh Kumar,
• Santanu Ghosh,
• Subhajit Bhunia and
• Alakesh Bisai

Beilstein J. Org. Chem. 2016, 12, 1153–1169, doi:10.3762/bjoc.12.111

• reaction of N-methyl arylamines and monoalkyl malonates/cyanoacetic acids. Under optimized conditions A and B, various β-N-arylamido esters and nitriles (3) were subjected to a one-pot alkylations using 1.2 equivalents of KOt-Bu to produce C-alkylated intermediate 5 followed by oxidative coupling using 1.2

Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes

• Adrián Gómez-Suárez,
• Yoshihiro Oonishi,
• Anthony R. Martin and
• Steven P. Nolan

Beilstein J. Org. Chem. 2016, 12, 172–178, doi:10.3762/bjoc.12.19

• as nitriles, ketones, esters, aldehydes, ketals, naphthyls, allyls or polyphenols, in a milder and more efficient manner than the previously reported methodologies. We have also identified that while we are able to use highly steric hindered phenols, small changes on the steric bulk of the alkynes

• methodology (Scheme 2). With that aim we reacted diphenylacetylene (1a) with several phenols, 2a–o, in toluene, using 0.5 mol % of [{Au(IPr)}2(µ-OH)][BF4] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) as the catalyst. Functional groups such as nitriles (3aa), ketones (3ab), esters (3ac), aldehydes

• . 50 substrates, thus demonstrating the robustness and synthetic versatility of the methodology. The protocol tolerates a wide range of functional groups, such as nitriles, ketones, esters, aldehydes, acetals, naphthyls or allyls. Furthermore, we have successfully used polyphenols in a milder and more

Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

• Bijay Shrestha and
• Ramesh Giri

Beilstein J. Org. Chem. 2015, 11, 2400–2407, doi:10.3762/bjoc.11.261

• on alkyl halides including highly sensitive esters (Table 2, entries, 5, 9 and 11), nitriles (Table 2, entries 6 and 7) and olefins (Table 2, entries 4, 8, 10, 13 and 15) [46]. With 10 mol % catalyst loading, the reaction can also be extended to the coupling of triarylaluminum reagents with benzyl

• electron-rich triarylaluminum reagents can be coupled with a variety of alkyl iodides and bromides containing a range of sensitive functional groups such as olefins, nitriles and esters, affording the alkylated arenes in good to excellent yields. Experimental General information. All the reactions and

A concise and efficient synthesis of benzimidazo[1,2-c]quinazolines through CuI-catalyzed intramolecular N-arylations

• Xinlong Pang,
• Chao Chen,
• Ming Li and
• Chanjuan Xi

Beilstein J. Org. Chem. 2015, 11, 2365–2369, doi:10.3762/bjoc.11.258

• nitriles. The reaction of o-cyanoaniline (1a), benzonitrile (1g) and di-(o-bromophenyl)iodonium salt 2 in the presence of Cu(OTf)2 gave the desired imine 3g together with imine 3a. After isolation of 3g it was further treated with 10 mol % of CuI in DMSO for 50 min to give product 4g in quantitative yield

Synthesis of D-fructose-derived spirocyclic 2-substituted-2-oxazoline ribosides

• Madhuri Vangala and
• Ganesh P. Shinde

Beilstein J. Org. Chem. 2015, 11, 2289–2296, doi:10.3762/bjoc.11.249

• in toluene through nucleophilic addition of electron-rich nitriles to the oxacarbenium ion intermediate of 1,2;3,4-di-O-isopropylidene-β-D-psicofuranose derivatives with concomitant intramolecular trapping of the C2 hydroxymethyl group on the electrophilic nitrilium carbon. These carbohydrate-derived

• therapeutics [11][12][13]. Traditionally, oxazolines are used as protecting groups in organic synthesis [14]. Several efficient methods for the construction of the 2-oxazoline functionality are reported in the literature from alkenes, carboxylic acid derivatives, nitriles [15][16][17][18][19], etc. In

• -protected 1,2-O-isopropylidene-β-D-fructofuranose derivatives with triflic acid (1.5 equiv) using nitriles (10 equiv) at −20 °C to rt in DCM [37]. Although fructopyranoses were shown to react with acetonitrile, propionitrile and benzonitrile, only one example of the corresponding fructofuranose with

Recent developments in copper-catalyzed radical alkylations of electron-rich π-systems

• Kirk W. Shimkin and
• Donald A. Watson

Beilstein J. Org. Chem. 2015, 11, 2278–2288, doi:10.3762/bjoc.11.248

• -withdrawing groups including esters, ketones and nitro groups were tolerated in the alkyl bromide coupling partner (Scheme 10). In addition, the reaction shows excellent functional group compatibility with respect to the styrene coupling partner, tolerating ethers, nitriles, chlorides and amines. Notably

• participated in the reaction, including those bearing esters, ketones, nitro and nitriles (Scheme 18). If the reaction was run in the presence of sodium iodide, vinyl iodides were produced. This protocol is complementary to Hu’s work in that it provides products of trans-carbohalogenation. In an elegant one

A convenient four-component one-pot strategy toward the synthesis of pyrazolo[3,4-d]pyrimidines

• Mingxing Liu,
• Jiarong Li,
• Hongxin Chai,
• Kai Zhang,
• Deli Yang,
• Qi Zhang and
• Daxin Shi

Beilstein J. Org. Chem. 2015, 11, 2125–2131, doi:10.3762/bjoc.11.229

• -carbonitrile with amides [18][19][20][21], carboxylic acids [22][23][24], amidines [25][26], nitriles [27][28], ketones [29][30] and halohydrocarbon [31], the cyclization of 5-aminopyrazole-4-carboxamides with amides [32], ureas [33][34][35][36], esters [37][38][39] and acyl chloride [40], and the reaction of

Chiral Cu(II)-catalyzed enantioselective β-borylation of α,β-unsaturated nitriles in water

• Lei Zhu,
• Taku Kitanosono,
• Pengyu Xu and
• Shū Kobayashi

Beilstein J. Org. Chem. 2015, 11, 2007–2011, doi:10.3762/bjoc.11.217

• -unsaturated nitriles in water. The catalyst system, which consisted of Cu(OAc)2 and a chiral 2,2′-bipyridine ligand, enabled β-borylation and chiral induction in water. Subsequent protonation, which was accelerated in aqueous medium, led to high activity of this asymmetric catalysis. Both solid and liquid

• substrates were suitable despite being insoluble in water. Keywords: carbon–boron bond formation; catalytic asymmetric synthesis; chiral copper(II) catalysis; β-hydroxy nitriles; Introduction In recent years, optically active organoboranes have attracted considerable attraction as versatile synthons for

• ]. Enantioselective boron conjugate addition to α,β-unsaturated nitriles provides one of the most efficient routes to chiral β-boryl nitriles. Several straightforward methods have been developed that rely on chiral Cu(I) complexes with air-sensitive phosphine ligands [11][12][13][14][15]. In contrast, Cu(II)-based

Copper-catalyzed aerobic radical C–C bond cleavage of N–H ketimines

• Ya Lin Tnay,
• Gim Yean Ang and
• Shunsuke Chiba

Beilstein J. Org. Chem. 2015, 11, 1933–1943, doi:10.3762/bjoc.11.209

• tetrahydropyranyl rings derived from nitriles 1c and 1d, respectively, afforded tricyclic oxaspirocyclohexadienones 3c and 3d in moderate yields along with the corresponding alkenes 4c and 4d as well as p-tolunitrile (5a) (Table 2, entries 2 and 3). On the other hand, the reaction starting from carbonitrile 1e