Synthetic terpenoids in the world of fragrances: Iso E Super^® is the showcase

• Alexey Stepanyuk and
• Andreas Kirschning

Beilstein J. Org. Chem. 2019, 15, 2590–2602, doi:10.3762/bjoc.15.252

• of years dating back well before biblical times [2][3]. Plants and resins served as source for perfumes after alcoholic extraction. These extracts were not only used as fragrances but also as medicine (aqua mirabilis), aphrodisiac and elixir of life (aquavitae). In 1882 'Fougere Royale' was created

A toolbox of molecular photoswitches to modulate the CXCR3 chemokine receptor with light

• Xavier Gómez-Santacana,
• Sabrina M. de Munnik,
• Tamara A. M. Mocking,
• Niels J. Hauwert,
• Shanliang Sun,
• Prashanna Vijayachandran,
• Iwan J. P. de Esch,
• Henry F. Vischer,
• Maikel Wijtmans and
• Rob Leurs

Beilstein J. Org. Chem. 2019, 15, 2509–2523, doi:10.3762/bjoc.15.244

• , Supporting Information File 1), preventing the extraction of accurate functional values. The PDE value, which reflects efficacies of both the trans and PSS form, appears to have an optimum for 6f (Figure 4B). Figure 4B also shows more subtle behavior for compounds 4d and 6e, which harbor a PDE value of 0.43

Current understanding and biotechnological application of the bacterial diterpene synthase CotB2

• Ronja Driller,
• Daniel Garbe,
• Norbert Mehlmer,
• Monika Fuchs,
• Keren Raz,
• Dan Thomas Major,
• Thomas Brück and
• Bernhard Loll

Beilstein J. Org. Chem. 2019, 15, 2355–2368, doi:10.3762/bjoc.15.228

• with residual organic waste streams, such as milling or forestry waste. Additionally, the heterologous terpene production minimizes waste generation as the targeted production of a single compound reduces extraction and purification steps [24][25]. Additionally, heterologous production enables protein

• engineering to optimize product ratios or to alter the native product portfolio of the enzyme [9][26][27]. Furthermore, production by engineered microorganisms considerably reduces the cost compared to total chemical synthesis or extraction from natural sources, since the target compounds are produced from

Isolation and biosynthesis of an unsaturated fatty acid with unusual methylation pattern from a coral-associated bacterium Microbulbifer sp.

• Amit Raj Sharma,
• Enjuro Harunari,
• Tao Zhou,
• Agus Trianto and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2019, 15, 2327–2332, doi:10.3762/bjoc.15.225

• sterilization. The inoculated flasks were incubated at 30 °C on a rotary shaker at 200 rpm for 5 days. Extraction and isolation After fermentation, 100 mL of 1-butanol was added to each production culture flask, and the flasks were allowed to shake for 1 h on a rotary shaker at 200 rpm. The mixture was

• 181.1230 [M − H]− (calcd for C11H17O2, 181.1229). Feeding experiment Feeding experiments were carried out using 13C-labeled precursors, sodium [1-13C]acetate and ʟ-[methyl-13C]methionine. The fermentation, extraction and purification of labeled compounds were performed in the same manner as describe for

Isolation of fungi using the diffusion chamber device FIND technology

• Benjamin Libor,
• Henrik Harms,
• Stefan Kehraus,
• Ekaterina Egereva,
• Max Crüsemann and
• Gabriele M. König

Beilstein J. Org. Chem. 2019, 15, 2191–2203, doi:10.3762/bjoc.15.216

• microorganisms (BCCM/IHEM, Brussels) by extracting DNA using their usual protocols and genomic DNA extraction kits and generation of partial sequences of DNA loci using standard primers of ITS1, ITS2, ITS4, 5.8S, RPBII, tef1α and β-tubulin. Digitalized and formatted DNA sequences were compared to reference

• (Leica, Wetzlar, Germany) and micromorphology was examined with an Olympus BX51 polarizing microscope (Olympus, Shinjuku, Japan) by analysis of conidia and mycelium to support the bioinformatic suggestions. Fermentation, extraction and isolation For cultivation of the marine isolates from the diffusion

Azologization and repurposing of a hetero-stilbene-based kinase inhibitor: towards the design of photoswitchable sirtuin inhibitors

• Christoph W. Grathwol,
• Nathalie Wössner,
• Sören Swyter,
• Adam C. Smith,
• Enrico Tapavicza,
• Robert K. Hofstetter,
• Anja Bodtke,
• Manfred Jung and
• Andreas Link

Beilstein J. Org. Chem. 2019, 15, 2170–2183, doi:10.3762/bjoc.15.214

• -30ADSF for liquid CO2 and two LC-20ADXR for modifier and make-up delivery), an on-line supercritical fluid extraction module (SFE-30A auto extractor equipped with 0.2 mL extraction vessels) for reaction monitoring, an autosampler (SIL-30AC) for purified compounds, a column thermostat (CTO-20AC) equipped

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

• final product (Figure 4). Interestingly, during the extraction process, compound 2 was detected at a retention time of 14.53 min and identified as esterified compound 1 (Figure 4 and Table S4, Supporting Information File 1). Using the metabolic engineering strategy, the product of Tvi09626 was

• represent the esterification reaction during the extraction process. The 5/6 bicyclic sesquiterpene identified and characterised in this study was a brasilane-type sesquiterpenoid; this sesquiterpenoid type is typically isolated from cultures of the basidiomycete Coltricia sideroides in combination with its

• characterised as a 5/6 bicyclic sesquiterpene compound 1 oxygenated at C-11. Interestingly, esterified compound 1 was isolated during the product extraction process, suggesting an esterification reaction. It contained a quaternary carbon with two methyl groups, which is uncommon of the cyclization mechanism of

Bipolenins K–N: New sesquiterpenoids from the fungal plant pathogen Bipolaris sorokiniana

• Chin-Soon Phan,
• Hang Li,
• Simon Kessler,
• Peter S. Solomon,
• Andrew M. Piggott and
• Yit-Heng Chooi

Beilstein J. Org. Chem. 2019, 15, 2020–2028, doi:10.3762/bjoc.15.198

• (Phenomenex, 2.6 µm, 2.1 × 100 mm), and semi-preparative C18 (Grace, 5 µm, 10 × 250 mm) were used. All solvents used for extraction were analytical grade, and solvents for HPLC were HPLC grade. Biological material The fungal strain B. sorokiniana BRIP10943 was obtained from Queensland Plant Pathology

• Herbarium (BRIP). It was isolated from a wheat field at Hermitage, QLD, Australia. The fungus was maintained on potato dextrose agar (PDA). Extraction and isolation B. sorokiniana was cultured on 16 plates of V8PDA at 25 °C for 14 days, then inoculated in 4 L shake-flask culture (25 °C, 180 rpm for 22 days

Isolation and characterisation of irinans, androstane-type withanolides from Physalis peruviana L.

• Annika Stein,
• Dave Compera,
• Bianka Karge,
• Mark Brönstrup and
• Jakob Franke

Beilstein J. Org. Chem. 2019, 15, 2003–2012, doi:10.3762/bjoc.15.196

• used in combination with the separation gradient described below. Extraction and isolation of withanolides 140 g of 9 weeks old, whole Physalis peruviana plants were frozen in liquid nitrogen and ground to a fine powder. The powder was extracted with 500 mL H2O/MeOH (3:1) at room temperature for 3 h

A review of the total syntheses of triptolide

• Xiang Zhang,
• Zaozao Xiao and
• Hongtao Xu

Beilstein J. Org. Chem. 2019, 15, 1984–1995, doi:10.3762/bjoc.15.194

• difficulty in extraction of 40 and 41 from the large quantity of alumina. Dehydration of the mixture of 40 and 41 in benzene quantitatively afforded a 1:2 mixture of 42 and its C-3 epimer 41. Reduction of the epimers with sodium borohydride and subsequent treatment with hydrochloric acid (2 N) gave single

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