Analysis of sesquiterpene hydrocarbons in grape berry exocarp (Vitis vinifera L.) using in vivo-labeling and comprehensive two-dimensional gas chromatography–mass spectrometry (GC×GC–MS)

• Philipp P. Könen and
• Matthias Wüst

Beilstein J. Org. Chem. 2019, 15, 1945–1961, doi:10.3762/bjoc.15.190

• measurement. The SPME extraction conditions were based on a slightly modified method described by Welke et al. [17]. Prior to SPME extraction, the samples were held at an incubation temperature of 45 °C for 10 min without stirring. The extraction was carried out at 45 °C for 30 min. After sampling the

Archangelolide: A sesquiterpene lactone with immunobiological potential from Laserpitium archangelica

• Silvie Rimpelová,
• Michal Jurášek,
• Lucie Peterková,
• Jiří Bejček,
• Vojtěch Spiwok,
• Miloš Majdl,
• Michal Jirásko,
• Miloš Buděšínský,
• Juraj Harmatha,
• Eva Kmoníčková,
• Pavel Drašar and
• Tomáš Ruml

Beilstein J. Org. Chem. 2019, 15, 1933–1944, doi:10.3762/bjoc.15.189

• archangelica Wulfen using supercritical CO2 extraction. We show that dansyl-archangelolide localizes in the endoplasmic reticulum of living cells similarly to trilobolide; localization in mitochondria was also detected. This led us to a more detailed study of the anticancer potential of archangelolide

• [12] was described, we aimed to develop a facile method for the isolation of these SLs from the seeds of Laserpitium archangelica Wulfen using supercritical CO2 extraction (SCE; for advantages of this method, see Supporting Information File 1, section 8). In our experience, any part of the plant may

• be used for extraction of compound 1, while the roots and seeds give much higher yields than other parts. Utilization of SCE gives improved efficiency of the extraction and shortens the work-up in contrast with classical methods. By the abovementioned methodology, we obtained sufficient amounts of

Halide metathesis in overdrive: mechanochemical synthesis of a heterometallic group 1 allyl complex

• Ross F. Koby,
• Nicholas R. Rightmire,
• Nathan D. Schley,
• Timothy P. Hanusa and
• William W. Brennessel

Beilstein J. Org. Chem. 2019, 15, 1856–1863, doi:10.3762/bjoc.15.181

• noted that both [KA'] and CsI are insoluble in hexanes, and the grinding clearly initiated a reaction that occurred before the first hexanes extraction. Structure of [CsKA'2] Small blocks grown from hexanes were identified from a single crystal X-ray study as the coordination polymer [CsKA'2]∞. A

Synthesis, enantioseparation and photophysical properties of planar-chiral pillar[5]arene derivatives bearing fluorophore fragments

• Guojuan Li,
• Chunying Fan,
• Guo Cheng,
• Wanhua Wu and
• Cheng Yang

Beilstein J. Org. Chem. 2019, 15, 1601–1611, doi:10.3762/bjoc.15.164

• from CuSO4 and sodium ascorbate through extraction with Et2O/water. Further purification of the crude product was carried out by silica gel column chromatography (dichloromethane/methanol 30:1) to afford P5A-DPA in 72% yield. The structure of P5A-DPA was characterized by 1H NMR, 13C NMR and high

Fluorine-containing substituents: metabolism of the α,α-difluoroethyl thioether motif

• Andrea Rodil,
• Alexandra M. Z. Slawin,
• Nawaf Al-Maharik,
• Ren Tomita and
• David O’Hagan

Beilstein J. Org. Chem. 2019, 15, 1441–1447, doi:10.3762/bjoc.15.144

• . Biotransformations and extraction conditions Culture media was purchased from Sigma-Aldrich. Each thioether (5–10 mg) was dissolved in DMF (50 µL) and inoculated into cultures of C. elegans. The cultures were incubated at 28 °C and 180 rpm for 72 h. Blank experiments were carried out in the absence of C. elegans

Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks

• Sebastian Hamer,
• Fynn Röhricht,
• Marius Jakoby,
• Ian A. Howard,
• Xianghui Zhang,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 1331–1338, doi:10.3762/bjoc.15.132

• cross coupling. Using this method, dicarboxylic acids could be obtained from simple aqueous work-up and extraction. Difluoro compound 1 Difluorobenzenes have been employed as dipolar rotors by Garcia-Garibay in crystals [10], as an elongated MOF linker by Blight and Forgan [25] and for the investigation

Genomics-inspired discovery of massiliachelin, an agrochelin epimer from Massilia sp. NR 4-1

• Jan Diettrich,
• Hirokazu Kage and
• Markus Nett

Beilstein J. Org. Chem. 2019, 15, 1298–1303, doi:10.3762/bjoc.15.128

• Bruker AV 600 MHz Avance III HD system with chloroform-d as solvent and internal standard. The solvent signals were referenced to δH 7.24 ppm and δC 77.0 ppm. Cultivation and extraction of Massilia sp. NR 4-1 Strain NR 4-1 was cultured in three 5 L Simax flasks each containing two liters of R2A medium

New terpenoids from the fermentation broth of the edible mushroom Cyclocybe aegerita

• Frank Surup,
• Florian Hennicke,
• Nadine Sella,
• Maria Stroot,
• Steffen Bernecker,
• Sebastian Pfütze,
• Marc Stadler and
• Martin Rühl

Beilstein J. Org. Chem. 2019, 15, 1000–1007, doi:10.3762/bjoc.15.98

• Drive Systems) at 23 °C. After one week of incubation the glucose concentration in the medium was tested daily. If no more free glucose could be found in the medium, the cultivation was extracted. Extraction The mycelium was separated from the fermentation broth with the help of a fluted filter. The

• rotary evaporator. The crude extract was dissolved in 4 mL methanol, evaporated under a nitrogen evaporator (VLM GmbH, Bielefeld, Germany) and stored in a freezer at −20 °C. The crude extract of the fermentation broth was obtained the same way. Isolation The crude extract obtained from the extraction was

• . The biomass and suspended substrates was separated by centrifugation. RNA extraction, cDNA synthesis and qPCR During fermentation, mycelial samples were taken at day 2, 4, 7, 9, 11 and 14 and stored in RNAlater (Qiagen, Venlo, Netherlands) until further use. Fungal mycelium was freeze-dried and ground

Heck- and Suzuki-coupling approaches to novel hydroquinone inhibitors of calcium ATPase

• Robert J. Kempton,
• Taylor A. Kidd-Kautz,
• Soizic Laurenceau and
• Stefan Paula

Beilstein J. Org. Chem. 2019, 15, 971–975, doi:10.3762/bjoc.15.94

• tissues are avoided. Compound 1b was found to be selectively toxic to PSA-producing prostate cancer cells as well as in animal studies at submicromolar concentrations [3]. Unfortunately, TG has been difficult to obtain: extraction yields from natural sources are low and the total synthesis of TG required

Synthesis of a novel category of pseudo-peptides using an Ugi three-component reaction of levulinic acid as bifunctional substrate, amines, and amino acid-based isocyanides

• Maryam Khalesi,
• Azim Ziyaei Halimehjani and
• Jürgen Martens

Beilstein J. Org. Chem. 2019, 15, 852–857, doi:10.3762/bjoc.15.82

• ; multicomponent; pseudo-peptides; Ugi reaction; Introduction The multistep synthesis of complex molecules normally requires a large number of repetitive synthetic operations, such as extraction, separation, chromatography and other purification steps. These disadvantages encouraged chemists to synthesize complex

Synthesis of acylglycerol derivatives by mechanochemistry

• Karen J. Ardila-Fierro,
• Andrij Pich,
• Marc Spehr,
• José G. Hernández and
• Carsten Bolm

Beilstein J. Org. Chem. 2019, 15, 811–817, doi:10.3762/bjoc.15.78

• fatty acids (e.g., chain length, degree of unsaturation, double bond position or stereochemistry), the access to pure DAGs and TAGs from natural sources by extraction is cumbersome. Alternatively, protected DAGs 5 can be chemically synthesized starting from glycerol [26] or glycidol [27], but either

Stereochemical investigations on the biosynthesis of achiral (Z)-γ-bisabolene in Cryptosporangium arvum

• Jan Rinkel and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2019, 15, 789–794, doi:10.3762/bjoc.15.75

• , Supporting Information File 1) and incubated with the common terpene precursors geranyl- (GPP, C10), farnesyl- (FPP, C15), geranylgeranyl- (GGPP, C20) and geranylfarnesyl (GFPP, C25) diphosphate. With hexane extraction and GC–MS analysis, only the incubation with FPP yielded a terpene product (Figure 2) that

New sesquiterpenoids from the South China Sea soft corals Clavularia viridis and Lemnalia flava

• Qihao Wu,
• Yuan Gao,
• Meng-Meng Zhang,
• Li Sheng,
• Jia Li,
• Xu-Wen Li,
• Hong Wang and
• Yue-Wei Guo

Beilstein J. Org. Chem. 2019, 15, 695–702, doi:10.3762/bjoc.15.64

• . viridis and L. flava are deposited at the Shanghai Institute of Materia Medica, CAS, under registration Nos. 13XS-49 and 13XS-52, respectively. Extraction and isolation The lyophilized bodies of C. viridis (80 g, dry weight) were minced into pieces and exhaustively extracted with acetone at room

Design and synthesis of multivalent α-1,2-trimannose-linked bioerodible microparticles for applications in immune response studies of Leishmania major infection

• Chelsea L. Rintelmann,
• Tara Grinnage-Pulley,
• Kathleen Ross,
• Daniel E. K. Kabotso,
• Angela Toepp,
• Anne Cowell,
• Christine Petersen,
• Balaji Narasimhan and
• Nicola Pohl

Beilstein J. Org. Chem. 2019, 15, 623–632, doi:10.3762/bjoc.15.58

• a handle for the incorporation of a fluorous-tag for ease of purification by fluorous solid phase-extraction (FSPE). The use of the fluorous tag enables solution-phase automated synthesis of α-1,2-trimannose in the future as shown previously with a related spacer and fluorous tag [47]. Incorporation

Low-budget 3D-printed equipment for continuous flow reactions

• Jochen M. Neumaier,
• Amiera Madani,
• Thomas Klein and
• Thomas Ziegler

Beilstein J. Org. Chem. 2019, 15, 558–566, doi:10.3762/bjoc.15.50

• could be used if precipitates are formed during a reaction which is often a problem in continuous flow reactions [33]. For mechanically mixing, a small magnetic stirring bar was placed in the reactor during printing. These reactors were used for the premixing of reactants or for the extraction steps

• photograph of the reaction with the reactor, the CSTR for extraction and a 10 mL syringe for phase separation is shown. It consists of two 3D-printed pumps for solutions of pentaacetylglucose in dichloromethane (1 M) and HBr in acetic acid (33%) and PP reactor R3. It should be noted that the reactor material

Syntheses and chemical properties of β-nicotinamide riboside and its analogues and derivatives

• Mikhail V. Makarov and
• Marie E. Migaud

Beilstein J. Org. Chem. 2019, 15, 401–430, doi:10.3762/bjoc.15.36

• with sodium methoxide in methanol. The triflate removal was conducted by an ion exchange step using a saturated aqueous solution of sodium chloride followed by an extraction with THF to remove the excess of nicotinamide and sodium trifluoromethanesulfonate byproducts (Scheme 7). The above described

Thiol-free chemoenzymatic synthesis of β-ketosulfides

• Adrián A. Heredia,
• Martín G. López-Vidal,
• Marcela Kurina-Sanz,
• Fabricio R. Bisogno and
• Alicia B. Peñéñory

Beilstein J. Org. Chem. 2019, 15, 378–387, doi:10.3762/bjoc.15.34

• CAL-B. It is worth noting that this amount represents a ≈8 fold decrease of used enzyme as compared to the corresponding small scale reaction (Table 2, entry 8). After 24 h, we were delighted to find that no enolester was detected by TLC monitoring, and after extraction and silica gel column

Silanediol versus chlorosilanol: hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes

• Falco Fox,
• Jörg M. Neudörfl and
• Bernd Goldfuss

Beilstein J. Org. Chem. 2019, 15, 167–186, doi:10.3762/bjoc.15.17

• hydrolyses and temperature resulting in further condensation products [50][51], leaves no comparison possible. At H2O/THF reflux conditions, the hydrolysis of dichlorosilane 13 yields silanediol 1 with >99% yield, after a reaction time of two seconds (Scheme 4, addition of H2O, with instant extraction with

Unexpected loss of stereoselectivity in glycosylation reactions during the synthesis of chondroitin sulfate oligosaccharides

• Teresa Mena-Barragán,
• José L. de Paz and
• Pedro M. Nieto

Beilstein J. Org. Chem. 2019, 15, 137–144, doi:10.3762/bjoc.15.14

• of a fluorous-assisted approach for the synthesis of CS oligosaccharides. The use of a fluorous tag allows the rapid isolation of fluorinated intermediates by performing a simple extraction from fluorous silica gel [27][28][29][30][31][32]. Moreover, this method maintains the advantages of solution

• intermediates by simple fluorous solid-phase extraction (F-SPE). Interestingly, the fluorous tag would be introduced by acylation using commercially available heptadecafluoroundecanoyl chloride and its deprotection would not involve any additional step at the end of the synthesis. N-Trifluoroacetyl (N-TFA

Fabrication of supramolecular cyclodextrin–fullerene nonwovens by electrospinning

• Hiroaki Yoshida,
• Ken Kikuta and
• Toshiyuki Kida

Beilstein J. Org. Chem. 2019, 15, 89–95, doi:10.3762/bjoc.15.10

• of C60 throughout the fibers. Two additional experiments were performed to confirm the presence of the CD–C60 inclusion complex indirectly. One investigated C60 extraction by toluene washing of the nonwovens. Toluene is a good solvent for C60, but UV–vis absorption peaks assignable to C60 are not

A convenient and practical synthesis of β-diketones bearing linear perfluorinated alkyl groups and a 2-thienyl moiety

• Ilya V. Taydakov,
• Yuliya M. Kreshchenova and
• Ekaterina P. Dolotova

Beilstein J. Org. Chem. 2018, 14, 3106–3111, doi:10.3762/bjoc.14.290

• extractants in solvent–solvent extraction processes [4], in preparation of volatile complexes for chemical vapour deposition (CVD) technique [5][6], in syntheses of luminescent compounds [7], as starting materials in organic and heterocyclic chemistry [8][9] and in many other practical applications [10][11

Volatiles from the hypoxylaceous fungi Hypoxylon griseobrunneum and Hypoxylon macrocarpum

• Jan Rinkel,
• Alexander Babczyk,
• Tao Wang,
• Marc Stadler and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2018, 14, 2974–2990, doi:10.3762/bjoc.14.277

• [11][12]. Fungal volatiles can be efficiently analysed by trapping, e.g., on charcoal filters with a closed-loop stripping apparatus (CLSA) that was developed by Grob and Zürcher [13], followed by filter extraction and GC–MS analysis of the obtained headspace extracts [14]. The unambiguous compound

N-Acylated amino acid methyl esters from marine Roseobacter group bacteria

• Hilke Bruns,
• Lisa Ziesche,
• Nargis Khakin Taniwal,
• Laura Wolter,
• Thorsten Brinkhoff,
• Jennifer Herrmann,
• Rolf Müller and
• Stefan Schulz

Beilstein J. Org. Chem. 2018, 14, 2964–2973, doi:10.3762/bjoc.14.276

• , interpretation of mass spectra, and verification by synthesis. Results and Discussion The secondary metabolites released by liquid cultures of various roseobacters were collected by extraction via Amberlite XAD-16 resin and analysed by GC/MS. Four of these strains, Roseovarius sp. D12_1.68 and Loktanella sp. F13

Synthesis of unnatural α-amino esters using ethyl nitroacetate and condensation or cycloaddition reactions

• Glwadys Gagnot,
• Vincent Hervin,
• Eloi P. Coutant,
• Sarah Desmons,
• Racha Baatallah,
• Victor Monnot and
• Yves L. Janin

Beilstein J. Org. Chem. 2018, 14, 2846–2852, doi:10.3762/bjoc.14.263

• proceeded in good yield, although care had to be taken during work-up as zinc complexes required the addition of an excess of ammonia to fully break in the course of the extraction. In an attempt to overcome the lack of condensation between ethyl nitroacetate (4) and electron-poor substrates 5j–l, we

Synthesis of a tyrosinase inhibitor by consecutive ethenolysis and cross-metathesis of crude cashew nutshell liquid

• Jacqueline Pollini,
• Valentina Bragoni and
• Lukas J. Gooßen

Beilstein J. Org. Chem. 2018, 14, 2737–2744, doi:10.3762/bjoc.14.252

• properties and industrial applications, for instance in surfactants, plasticizers, resins, soft materials and diverse medical applications [7]. Isolated via cold-press or solvent extraction processes, it contains predominantly anacardic acid (1). Upon distillation or any other thermal treatment, anacardic

• is added in excess. The main difficulty is that thermal purification of CNSL would inevitably lead to decarboxylation, and that unpurified CNSL, as it is obtained in an extraction process, contains a wealth of side components, many of which act as catalyst poisons. However, if an ethenolysis could be

• -hexene followed by a hydrogenation and thus, selectively obtain the target product 2-hydroxy-6-tridecylbenzoic acid (3). Results and Discussion Ethenolysis of crude CNSL After thorough optimization, we found that natural CNSL, a highly viscous brown oil, obtained by ether extraction of cashew nutshells