Genome mining in Trichoderma viride J1-030: discovery and identification of novel sesquiterpene synthase and its products

• Xiang Sun,
• You-Sheng Cai,
• Yujie Yuan,
• Guangkai Bian,
• Ziling Ye,
• Zixin Deng and
• Tiangang Liu

Beilstein J. Org. Chem. 2019, 15, 2052–2058, doi:10.3762/bjoc.15.202

• two new alkane derivatives colisiderin A and (7E,9E)-undeca-7,9-diene-2,4,5-triol [35] and from the organic extract of the red alga Laurencia obtusa [36]. However, to the best of our knowledge, ours is the first report of these brasilane-type sesquiterpenes obtained via biosynthetic genes. Metal ion

Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings

• Manuel Pedrón,
• Laura Legnani,
• Maria-Assunta Chiacchio,
• Pierluigi Caramella,
• Tomás Tejero and
• Pedro Merino

Beilstein J. Org. Chem. 2019, 15, 1552–1562, doi:10.3762/bjoc.15.158

• particular, those involving ruthenium tetroxide [3][4] occupy a privileged position among the modern oxidation methods due to their versatility regarding functional groups that can be oxidized and formed [5]. Alkane functionalization continues to be a current challenge in organic synthesis [6] and oxidation

• typically performed by preparing ruthenium tetroxide in situ from ruthenium species in lower oxidation states (RuCl3 or RuO2) and an oxidant such as NaIO4 [8]. Under these conditions RuO4 reacts with the alkane to form intermediate species I that evolves to the alcohol and RuO3, which is re-oxidized to re

• between RuO4 and the alkane, and it has been studied both experimentally and computationally having some initial controversy. The first studies were reported by Bakke et al. in 1986 who suggested the formation of intermediate ionic species on the basis of kinetic isotopic effects and solvent and

Formation of an unexpected 3,3-diphenyl-3H-indazole through a facile intramolecular [2 + 3] cycloaddition of the diazo intermediate

• Andrew T. King,
• Hugh G. Hiscocks,
• Lidia Matesic,
• Mohan Bhadbhade,
• Roger Bishop and
• Alison T. Ung

Beilstein J. Org. Chem. 2019, 15, 1347–1354, doi:10.3762/bjoc.15.134

• calculated positions. However, since these are well-defined Ar–H groups, their positional errors will be relatively small. Over recent years much understanding has been gained of dihydrogen bonding X–H···H–Y [18][19]. Close examination has been made of the alkane C–H···H–C contact, particularly for reactive

Precious metal-free molecular machines for solar thermal energy storage

• Meglena I. Kandinska,
• Snejana M. Kitova,
• Vladimira S. Videva,
• Stanimir S. Stoyanov,
• Stanislava B. Yordanova,
• Stanislav B. Baluschev,
• Silvia E. Angelova and
• Aleksey A. Vasilev

Beilstein J. Org. Chem. 2019, 15, 1096–1106, doi:10.3762/bjoc.15.106

• TDPBE0 spectra in ACN for dye 4b and its Ba2+ complex. Quaternization of 2-methylbenzothiazoles with alkane sultones. Synthesis of 4-(aza-15-crown-5)benzocarbaldehyde (3) [22]. Synthesis of dyes 4a–d. Absorption maxima (λmax,abs), fluorescence emission maxima (λmax,f), shift of the absorption maxima

Adhesion, forces and the stability of interfaces

• Robin Guttmann,
• Johannes Hoja,
• Christoph Lechner,
• Reinhard J. Maurer and
• Alexander F. Sax

Beilstein J. Org. Chem. 2019, 15, 106–129, doi:10.3762/bjoc.15.12

• ., when a large n-alkane changes from the linear to the hairpin structure; non-covalent interaction, on the other hand, does not exclude creation and stabilization of cation–anion pairs or zwitterions and their stabilization by Coulomb interaction. Weak molecular interaction is certainly the best term for

• among alkane molecules in liquid alkanes gives a strong favorable transfer energy for passage of an alkane from vapor into liquid alkane”, explaining the poor solubility of hydrocarbons in water and the good solubility of alkane molecules in liquid alkane [11]. Nonetheless, this interaction is nothing

• stabilization of parallel alkane chains, as well as the stabilization of aromatic molecules adsorbed to graphene or carbon nanotubes. Furthermore, we found that the stabilization energy of an adsorbent and several small adsorbate molecules increases when the latter are in close contact with each other. This

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