Reactions of 3-(p-substituted-phenyl)-5-chloromethyl-1,2,4-oxadiazoles with KCN leading to acetonitriles and alkanes via a non-reductive decyanation pathway

• Akın Sağırlı and
• Yaşar Dürüst

Beilstein J. Org. Chem. 2018, 14, 3011–3017, doi:10.3762/bjoc.14.280

• temperature plays a significant role upon formation of it and in situ-formed HCN facilitates the decyanation (nitrile–alkane conversion) possibly since it is the only proton source in the reaction medium. This unfamiliar decyanation reaction presumably proceeds through product 3. First, in the presence of CN

• nitrile group into an alkane by using KCN–HCN associates through a possible release of cyanogen which is not detected or isolated. This synthetic protocol seems to be applicable for further decyanation processes containing a 1,2,4-oxadiazole moiety. Synthesis of mono- or dialkylated acetonitriles

Hydroarylations by cobalt-catalyzed C–H activation

• Rajagopal Santhoshkumar and
• Chien-Hong Cheng

Beilstein J. Org. Chem. 2018, 14, 2266–2288, doi:10.3762/bjoc.14.202

• . Based on the mechanistic studies, a possible reaction mechanism for the hydroarylation reaction was proposed in Scheme 9. The reaction begins with the generation of an ambiguous low-valent cobalt catalyst from the reaction of CoBr2, ligand and Grignard reagent, which gives the alkane and MgX2 as the by

Preparation and X-ray structure of 2-iodoxybenzenesulfonic acid (IBS) – a powerful hypervalent iodine(V) oxidant

• Irina A. Mironova,
• Pavel S. Postnikov,
• Rosa Y. Yusubova,
• Akira Yoshimura,
• Thomas Wirth,
• Viktor V. Zhdankin,
• Victor N. Nemykin and
• Mekhman S. Yusubov

Beilstein J. Org. Chem. 2018, 14, 1854–1858, doi:10.3762/bjoc.14.159

• to the respective carbonyl compounds with Oxone® (2KHSO5·KHSO4·K2SO4) in nitromethane, acetonitrile, or ethyl acetate [13]. Recent research has revealed the extreme activity of IBS as a catalyst in numerous other oxidations, such as: the oxidation of benzylic and alkane C–H bonds [14], the oxidation

An overview of recent advances in duplex DNA recognition by small molecules

• Sayantan Bhaduri,
• Nihar Ranjan and
• Dev P. Arya

Beilstein J. Org. Chem. 2018, 14, 1051–1086, doi:10.3762/bjoc.14.93

Two novel blue phosphorescent host materials containing phenothiazine-5,5-dioxide structure derivatives

• Feng-Ming Xie,
• Qingdong Ou,
• Qiang Zhang,
• Jiang-Kun Zhang,
• Guo-Liang Dai,
• Xin Zhao and
• Huai-Xin Wei

Beilstein J. Org. Chem. 2018, 14, 869–874, doi:10.3762/bjoc.14.73

• energy level and good stability, herein, with phenothiazine-5,5-dioxide as acceptor (A) and carbazole as donor (D), and introducing an alkane chain group to the host materials for better film-forming properties, two novel blue phosphorescent host materials, CEPDO and CBPDO, were synthesized. At the same

Cobalt-catalyzed directed C–H alkenylation of pivalophenone N–H imine with alkenyl phosphates

• Wengang Xu and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2018, 14, 709–715, doi:10.3762/bjoc.14.60

• cycle illustrated in Scheme 5. An alkylcobalt species A, generated from the cobalt precatalyst and the Grignard reagent, would undergo cyclometalation of magnesium alkylidene amide 1·MgX, generated from imine 1 and the Grignard reagent, to give a cobaltacycle species B while liberating an alkane R–H

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry

• Katharina Hiebler,
• Georg J. Lichtenegger,
• Manuel C. Maier,
• Eun Sung Park,
• Renie Gonzales-Groom,
• Bernard P. Binks and
• Heidrun Gruber-Woelfler

Beilstein J. Org. Chem. 2018, 14, 648–658, doi:10.3762/bjoc.14.52

• catalyst particles first dispersed in water using an ultrasonic probe (Jencons Vibra-Cell, 5 min, 130 W). The oils chosen are the aliphatic alkane octane (Sigma, >99%, density 0.699 g/cm3), the cyclic alkane cyclohexane (Fisher Scientific, >99%, density 0.774 g/cm3) and the aromatic oil toluene (VWR

An alternative to hydrogenation processes. Electrocatalytic hydrogenation of benzophenone

• Cristina Mozo Mulero,
• Alfonso Sáez,
• Jesús Iniesta and
• Vicente Montiel

Beilstein J. Org. Chem. 2018, 14, 537–546, doi:10.3762/bjoc.14.40

• alcohol or alkane derivatives. Table 1 also depicts the average cell voltage from the electrocatalytic hydrogenation of benzophenone, with values of 0.2, 0.3 and 0.5 V for 10, 15 and 20 mA cm−2, respectively. More precisely, Figure 6 plots cell voltage versus time at 10 mA cm−2. In this case, a high cell

• diphenylmethanol is still over 90% irrespectively of the current density examined; the alcohol and alkane derivatives are also obtained, though prevailing the diphenylmethanol with high product yield (see Figure 8), being similar behaviour as that shown for the electrochemical hydrogenation using the Pd0.02/C/T

Acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicyclo[2.2.1]hept-5-ene with alcohols

• Katrina Tait,
• Alysia Horvath,
• Nicolas Blanchard and
• William Tam

Beilstein J. Org. Chem. 2017, 13, 2888–2894, doi:10.3762/bjoc.13.281

• includes the reduction to form alkane 8 [3], oxidative cleavage of the C=C bond to form 9 [4], ring-opening metathesis to form functionalized alkenes 10 and 11 [4], dihydroxylation to form diol 12 [5], ruthenium-catalyzed [2 + 2] cycloaddition with unsymmetrical alkynes to form regioisomers 13 and 14 [6

Dialkyl dicyanofumarates and dicyanomaleates as versatile building blocks for synthetic organic chemistry and mechanistic studies

• Grzegorz Mlostoń and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2017, 13, 2235–2251, doi:10.3762/bjoc.13.221

• starting fumarate [67]. Differently substituted piperazin-2-ones can be efficiently prepared by reacting dialkyl dicyanofumarates E-1 with alkane or cycloalkane-1,2-diamines. For example, the reaction with trans-cyclohexane-1,2-diamine (72) performed in acetonitrile at room temperature for 30 min gave the

Construction of highly enantioenriched spirocyclopentaneoxindoles containing four consecutive stereocenters via thiourea-catalyzed asymmetric Michael–Henry cascade reactions

• Yonglei Du,
• Jian Li,
• Kerong Chen,
• Chenglin Wu,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2017, 13, 1342–1349, doi:10.3762/bjoc.13.131

• derivatives with good enantiomeric excess (ee) values, respectively. However, the utility of the reaction is limited to α,β-unsaturated aldehydes with aromatic/alkane substitutions and nitroolefins with aromatic substitutions. Additionally, Shao’s group (Scheme 1, reaction 1C) developed a one-pot thiourea

Contribution of microreactor technology and flow chemistry to the development of green and sustainable synthesis

• Flavio Fanelli,
• Giovanna Parisi,
• Leonardo Degennaro and
• Renzo Luisi

Beilstein J. Org. Chem. 2017, 13, 520–542, doi:10.3762/bjoc.13.51

• traditional batch chemistry for safety reason. Kappe and co-workers recently developed a reduction of the alkene to the corresponding alkane, by a catalyst-free generation of diimide by oxidation of hydrazine monohydrate (N2H4·H2O) with molecular oxygen [89][90]. The flow system set-up is reported in Scheme

Continuous N-alkylation reactions of amino alcohols using γ-Al₂O₃ and supercritical CO₂: unexpected formation of cyclic ureas and urethanes by reaction with CO₂

• Emilia S. Streng,
• Darren S. Lee,
• Michael W. George and
• Martyn Poliakoff

Beilstein J. Org. Chem. 2017, 13, 329–337, doi:10.3762/bjoc.13.36

• the presence of scCO2 and thus proceeds faster than the intermolecular reaction. We also explored the cyclisation and N-alkylation of different amino alcohol substrates. Initially we investigated the effect of simply changing the alkane chain length. Starting with 4-amino-1-butanol (3) under the model

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

Diels–Alder reactions of myrcene using intensified continuous-flow reactors

• Christian H. Hornung,
• Miguel Á. Álvarez-Diéguez,
• Thomas M. Kohl and
• John Tsanaktsidis

Beilstein J. Org. Chem. 2017, 13, 120–126, doi:10.3762/bjoc.13.15

• into a Vapourtec R2/R4 flow reactor set-up [26], consisting of two 1.0 mm i.d. perfluoroalkoxy alkane (PFA) reactor coil modules in series (10 mL each – total reactor volume: 20 mL). The pump flow rate of the myrcene solution was set to 0.3 mL∙min−1, the pump flow rate of the acrylic acid solution was

Benzothiadiazole oligoene fatty acids: fluorescent dyes with large Stokes shifts

• Lukas J. Patalag and
• Daniel B. Werz

Beilstein J. Org. Chem. 2016, 12, 2739–2747, doi:10.3762/bjoc.12.270

• with very similar geometrical parameters differing only in their absorption and emission wavelengths. The grade of unsaturation as the sole geometrical difference thus provides a set of probes to study the effect of rigidified ethene moieties as straight-chain alkane surrogates within biological

A self-assembled cyclodextrin nanocarrier for photoreactive squaraine

• Ulrike Kauscher and
• Bart Jan Ravoo

Beilstein J. Org. Chem. 2016, 12, 2535–2542, doi:10.3762/bjoc.12.248

• . Additionally hexyl alkane chains were introduced on both N-termini. Santos et al. showed that these lead to a higher intersystem crossing compared to shorter alkane chains [20][21]. The analytical data for AdSq (see Supporting Information File 1) are consistent with the molecular structure shown in Figure 1

Methylpalladium complexes with pyrimidine-functionalized N-heterocyclic carbene ligands

• Dirk Meyer and
• Thomas Strassner

Beilstein J. Org. Chem. 2016, 12, 1557–1565, doi:10.3762/bjoc.12.150

• complexes were fully characterized by standard methods and in three cases also by a solid state structure. Keywords: alkane activation; alkyl complex; NHC; palladium; solid state structure; Introduction Palladium complexes have been shown to be versatile homogeneous catalysts in a variety of reactions [1

• mechanism and potential intermediates. Quantum chemical (QC) investigations have been very helpful during the last years in elucidating the mechanisms of palladium-catalyzed reactions [26][36]. According to our QC calculations the catalytic cycle for the alkane activation by bis(NHC) palladium complexes

Recent advances in C(sp³)–H bond functionalization via metal–carbene insertions

• Bo Wang,
• Di Qiu,
• Yan Zhang and
• Jianbo Wang

Beilstein J. Org. Chem. 2016, 12, 796–804, doi:10.3762/bjoc.12.78

• (I) complexes. In some cases, high regioselectivity and enantioselectivity have been achieved in the C–H bond insertion of small alkanes. This review highlights the most recent accomplishments in this field. Keywords: alkane; diazo compounds; C–H bond functionalization; C–H bond insertion; metal

• chiral porphyrins D4-por*, the enantioselective intermolecular carbene insertion into C(sp3)–H bonds was achieved with moderate to high selectivities (Scheme 7). Besides, the reaction of diazo compounds with benzylic, allylic and alkane C(sp3)–H bonds afforded the insertion products in up to 80% yield

• and Etienne reported a perfluorinated F21-tris(pyrazoly)borate (F21-Tp) scorpionate ligand, which enhanced alkane C–H functionalization by carbene insertion with (F21-Tp)Cu and (F21-Tp)Ag catalysts (Figure 1) [38]. In particular, with silver catalyst remarkably low catalyst loading (ca. 0.5%), and

From steroids to aqueous supramolecular chemistry: an autobiographical career review

• Bruce C. Gibb

Beilstein J. Org. Chem. 2016, 12, 684–701, doi:10.3762/bjoc.12.69

• change the shape of the pocket by reducing the width of the portal but increasing its depth. The result is a host with approximately the same carrying capacity as octa-acid, but very different binding and assembly properties. For example, the binding profile of octa-acid using the metric of n-alkane

• -alkane guests are examined [50]. This reduced propensity of TEMOA to dimerize means that when the guest is as large as C17H36, rather than form a dimer the cavitand switches to a tetrameric, pseudo-tetrahedral, 4:2 host–guest complex (Figure 14) [51]. This is possible because the methyl groups that

Thermal and oxidative stability of Atlantic salmon oil (Salmo salar L.) and complexation with β-cyclodextrin

• Daniel I. Hădărugă,
• Mustafa Ünlüsayin,
• Alexandra T. Gruia,
• Cristina Birău (Mitroi),
• Gerlinde Rusu and
• Nicoleta G. Hădărugă

Beilstein J. Org. Chem. 2016, 12, 179–191, doi:10.3762/bjoc.12.20

• meaty fish parts were used for oil extraction. GC-grade hexane (Sigma-Aldrich) was the main solvent used for raw and degraded fish oil dilutions. The Supelco 37 Component FAME mix (Sigma-Aldrich) and C8–C20 alkane standard solution (Fluka Chemie AG) were the main tools for identifying the FAMEs in

• NIST/EPA/NIH Mass Spectral Library 2.0 (2002), by using the FAMEs 37 standard mixture analyzed under the same conditions and by comparing the Kovats indices (obtained with the C8–C20 alkane standard) for the known FAMEs for this GC column type. The acquisition and handling of the GC–MS data was

Preparation of Pickering emulsions through interfacial adsorption by soft cyclodextrin nanogels

• Shintaro Kawano,
• Toshiyuki Kida,
• Mitsuru Akashi,
• Hirofumi Sato,
• Motohiro Shizuma and
• Daisuke Ono

Beilstein J. Org. Chem. 2015, 11, 2355–2364, doi:10.3762/bjoc.11.257

• using an n-alkane/water system [12]. They reported that the most stable emulsion is formed by β-CD–oil complexes when the contact angles are close to 90° at the oil–water interface. Davarpanah et al. examined the relationship between the stability of O/W Pickering emulsions formed through complexation

Recent advances in copper-catalyzed C–H bond amidation

• Jie-Ping Wan and
• Yanfeng Jing

Beilstein J. Org. Chem. 2015, 11, 2209–2222, doi:10.3762/bjoc.11.240

• ). While most known literature methods in the copper-catalyzed alkane amidation focused on the transformation of either benzylic, allylic C–H bonds or C–H bonds adjacent to nitrogen or oxygen atoms, the amidation of unactivated C–H bonds in simple linear or cyclic alkanes remained as a challenge. Recently

• bond was not favored. More notably, the exploration on the reaction mechanism disclosed that the activation of the alkyl C–H bond was initiated by the tert-butoxy radical (Scheme 6). Inspired by the alkane C–H activation, Yu and Cheng et al. [51] discovered that directly heating amides in cyclohexane

• the reaction in the synthesis of indoles was later achieved by mean of ligand-free condition via the co-catalysis of Cu(eh)2 (copper(II) 2-ethylhexanoate) and TEMPO under oxygen atmosphere [68]. C(sp)–H bond amidation The C(sp)–H bond in terminal alkynes is more acidic than equivalent alkane and

C–H bond halogenation catalyzed or mediated by copper: an overview

• Wenyan Hao and
• Yunyun Liu

Beilstein J. Org. Chem. 2015, 11, 2132–2144, doi:10.3762/bjoc.11.230

• convert smoothly (Scheme 24). Besides catalyzing the halogenation of inactive alkane substrates via a typical C–H activation, copper catalysis also exhibited important application in the electrophilic halogenation of some active methylene substrates such as ketones or esters. Although these active

Preparative semiconductor photoredox catalysis: An emerging theme in organic synthesis

• David W. Manley and
• John C. Walton

Beilstein J. Org. Chem. 2015, 11, 1570–1582, doi:10.3762/bjoc.11.173

• product (toluene, 38). Diphenylacetic acid yielded tetraphenylethane in a near-quantitative yield but in contrast, the related 9H-fluorene-9-carboxylic acid produced the reduced alkane (9H-fluorene) as the major product. Incorporation of substituents on the phenyl ring proved a success; arylacetic acids