Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions

• Paul P. Kelly,
• Anja Eichler,
• Susanne Herter,
• David C. Kranz,
• Nicholas J. Turner and
• Sabine L. Flitsch

Beilstein J. Org. Chem. 2015, 11, 1713–1720, doi:10.3762/bjoc.11.186

• libraries I–VII and the Tyr96Phe parent with A) ethylbenzene (5), B) the para-methylated derivative 6 and C) the para-brominated derivative 7. Reaction conditions: 180 mg/mL cells, 1 mM substrates, 50 mM sodium phosphate buffer (pH 7.2, 100 mM KCl, 0.4% glycerol (v/v)), 20 °C, 250 rpm, 48 h. Product yields

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

• Ivan Bassanini,
• Karl Hult and
• Sergio Riva

Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174

• activated 2,2,2-trichloroethyl diester of (±)-3,4-epoxyadipic acid. The stereoselectivity of porcine pancreatic lipase discriminated between the two enantiomers and afforded the chiral (−)-polyester with molecular weight of 7900 Dalton (Figure 9). Yang et al. compared the polymerization of glycerol and a

• . Polyesters containing epoxy moieties. Biocatalyzed synthesis of polyesters containing glycerol. Iataconic (34) and malic (35) acid. Oxidized poly(hexanediol-2-mercaptosuccinate) polymer. C-5-substituted isophthalates. Curcumin-based polyesters. Silylated polyesters. Polyesters containing reactive ether

Multivalent polyglycerol supported imidazolidin-4-one organocatalysts for enantioselective Friedel–Crafts alkylations

• Tommaso Pecchioli,
• Manoj Kumar Muthyala,
• Rainer Haag and
• Mathias Christmann

Beilstein J. Org. Chem. 2015, 11, 730–738, doi:10.3762/bjoc.11.83

• bearing a G1 glycerol dendron tail was also prepared for comparison with the multivalent systems 4a–c and evaluation of the possible presence of cooperative effects (Scheme 1). Polyglycerol 1 (Mn = 9000 g/mol, loading OH = 13.5 mmol/g, PDI = 1.87) was obtained following a previously reported procedure by

Exploring monovalent and multivalent peptides for the inhibition of FBP21-tWW

• Lisa Maria Henning,
• Sumati Bhatia,
• Miriam Bertazzon,
• Michaela Marczynke,
• Oliver Seitz,
• Rudolf Volkmer,
• Rainer Haag and
• Christian Freund

Beilstein J. Org. Chem. 2015, 11, 701–706, doi:10.3762/bjoc.11.80

• literature [19]. The transformation started from the mesylation of the hydroxy groups on the hPG. In the next step, the mesylated polyglycerol was converted to poly(glycerol azide). In the last step, azide functionalities (N3) were reduced to primary amines (-NH2) via Staudinger reduction to obtain the

An integrated photocatalytic/enzymatic system for the reduction of CO₂ to methanol in bioglycerol–water

• Michele Aresta,
• Angela Dibenedetto,
• Tomasz Baran,
• Antonella Angelini,
• Przemysław Łabuz and
• Wojciech Macyk

Beilstein J. Org. Chem. 2014, 10, 2556–2565, doi:10.3762/bjoc.10.267

• regeneration process is enhanced by using a Rh(III)-complex for facilitating the electron and hydride transfer from the H-donor (water or a water–glycerol solution) to NAD+. This resulted in the production of 100 to 1000 mol of CH3OH from one mol of NADH, providing the possibility for practical application

• was evidenced by measuring the amount of photogenerated 1,4-NADH using water or water/glycerol as electron donor. Figure 3b illustrates the results of the photocatalytic regeneration of NADH in presence of various materials after 6 hours of irradiation. Interestingly, for [CrF5(H2O)]2−@TiO2 the yield

• rhodium complex (according to Equation 1), is thus thermodynamically feasible. The photogenerated holes can regain electrons via the oxidation of glycerol. The reduced complex (Rh(I)) reacts with a proton yielding a Rh(III)-hydrido species (Equation 2). The resulting Rh-hydrido-species transfers the

Synthesis of phosphoramidites of isoGNA, an isomer of glycerol nucleic acid

• Keunsoo Kim,
• Venkateshwarlu Punna,
• Phaneendrasai Karri and
• Ramanarayanan Krishnamurthy

Beilstein J. Org. Chem. 2014, 10, 2131–2138, doi:10.3762/bjoc.10.220

• Keunsoo Kim Venkateshwarlu Punna Phaneendrasai Karri Ramanarayanan Krishnamurthy Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Rd, La Jolla, CA 92037, USA 10.3762/bjoc.10.220 Abstract IsoGNA, an isomer of glycerol nucleic acid GNA, is a flexible (acyclic

• the adenine derivative. The synthetic improvements described here enable an easy access to isoGNA and allows for the further exploration of this structural unit in oligonucleotide chemistry thereby spurring investigations of its usefulness and applicability. Keywords: acyclic nucleic acids; glycerol

• recently reported on the base-pairing properties of isoGNA, an isomer of glycerol derived nucleic acid (Figure 1) [8]. Our motivation was driven by the question “how structurally simple and minimal can an oligonucleotide be and still exhibit base-pairing?” When we studied isoGNA we were surprised to find

Postsynthetic functionalization of glycodendrons at the focal point

• Thisbe K. Lindhorst and
• Katharina Elsner

Beilstein J. Org. Chem. 2014, 10, 1482–1487, doi:10.3762/bjoc.10.152

• for incorporation into lipid bilayers, the di- and tetravalent glycodendrons 6 and 9 were then cross-coupled with the mono-allylated glycerol triether 22 (Scheme 4). The alkene 22 can be derived from commercially available glycerolmonoallyl ether according to the literature [15]. Metathesis with the

• divalent glycodendron 6 led to the desired product 23 as cis/trans mixture in 38% yield, while the glycerol ether dimer was obtained as the main product (not shown). The analogous result was obtained with the tetravalent glycodendron 9 leading to the hetero-cross coupling product 24 as the minor and the

Continuous flow nitration in miniaturized devices

• Amol A. Kulkarni

Beilstein J. Org. Chem. 2014, 10, 405–424, doi:10.3762/bjoc.10.38

Physalin H from Solanum nigrum as an Hh signaling inhibitor blocks GLI1–DNA-complex formation

• Midori A. Arai,
• Kyoko Uchida,
• Samir K. Sadhu,
• Firoj Ahmed and
• Masami Ishibashi

Beilstein J. Org. Chem. 2014, 10, 134–140, doi:10.3762/bjoc.10.10

• Chemiluminescent EMSA Kit (Thermo). The binding reaction was set up as follows: 70 ng of GST–GLI1 protein, biotin-labeled GLI1–BS (20 fmol), and compound in DMSO (final DMSO concentration was 0.6%) were combined in 2 μL of 10 × binding buffer (kit), (5 mM MgCl2, 4% glycerol) on ice (total volume 20 μL). After

SF002-96-1, a new drimane sesquiterpene lactone from an Aspergillus species, inhibits survivin expression

• Silke Felix,
• Louis P. Sandjo,
• Till Opatz and
• Gerhard Erkel

Beilstein J. Org. Chem. 2013, 9, 2866–2876, doi:10.3762/bjoc.9.323

• prepared by lysing the cells with Totex buffer (20 mM HEPES, pH 7.4, 350 mM NaCl, 20% glycerol, 1% NP-40, 1 mM MgCl2, 0.5 mM EDTA, 0.1 mM EGTA, 0.5 mM DTT, 10 mM β-glycerophosphate, 10 mM NaF, 1 mM Na3VO4, 1:25 complete protease-inhibitor cocktail according to the manufacturer´s recommendation (Roche

• freezing step at −80 °C and rethawing, the cell lysate was centrifuged at 1000g for 10 min at 4 °C. 25 µL of the supernatants were transferred into a new 96-well plate and incubated with 75 µL assay buffer (50 mM HEPES, 100 mM NaCl, 0.1% CHAPS, 10 mM DTT, 1 mM EDTA, 10% glycerol, pH: 7.4) containing 20 µM

[²H₂₆]-1-epi-Cubenol, a completely deuterated natural product from Streptomyces griseus

• Christian A. Citron and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2013, 9, 2841–2845, doi:10.3762/bjoc.9.319

• : 1000 mL) for a control of terpene production under normal growth conditions, or fully deuterated minimal medium (DMM, [2H8]glycerol: 5 mL, (N2H4)SO4: 1.0 g, K2[2H]PO4: 0.5 g, MgSO4·7[2H2]O: 0.2 g, FeSO4·7[2H2]O: 0.01 g, agar: 12.0 g, [2H2]O: 1000 mL) to obtain [2H26]-3. DMM liquid culture medium was

• devoid of agar and CaCO3. Deuterated [2H8]glycerol (99% 2H) was obtained from Eurisotop (Saarbrücken, Germany), deuterium oxide (99.9% 2H) was obtained from Deutero GmbH (Kastellaun, Germany), and all deuterated hydrated salts were obtained by dissolving the non-deuterated analogs in a large excess of

Oligomeric epoxide–amine adducts based on 2-amino-N-isopropylacetamide and α-amino-ε-caprolactam: Solubility in presence of cyclodextrin and curing properties

• Julian Fischer and
• Helmut Ritter

Beilstein J. Org. Chem. 2013, 9, 2803–2811, doi:10.3762/bjoc.9.315

• Julian Fischer Helmut Ritter Institute of Organic Chemistry and Macromolecular Chemistry, Heinrich-Heine-University Düsseldorf, Universitätsstraße 1, D-40225 Düsseldorf, Germany 10.3762/bjoc.9.315 Abstract 2-Amino-N-isopropylacetamide and α-amino-ε-caprolactam were reacted with glycerol

• reactivity of the primary amine group towards epoxides due to the formation of activating hydrogen bonds. The subsequent epoxide–amine polyaddition was carried out with glycerol diglycidyl ether (8), which was directly used as a mixture of the structural isomers 8a and 8b. To facilitate the following

• around 1–3 thousands. Interestingly, the calculated values due to Carothers’ equation (1.2-fold excess of the amine, complete conversion) gave an average molecular weight of 1760 g/mol for 9 and 1826 g/mol for 10, respectively. Conclusion Two novel water soluble and thermoresponsive glycerol diglycidyl

Biosynthesis of rare hexoses using microorganisms and related enzymes

• Zijie Li,
• Yahui Gao,
• Hideki Nakanishi,
• Xiaodong Gao and
• Li Cai

Beilstein J. Org. Chem. 2013, 9, 2434–2445, doi:10.3762/bjoc.9.281

• stereoselectively synthesize D-psicose. The donor molecule DHAP, a highly expensive starting material ($970.00/250 mg, Sigma-Aldrich), was generated in situ from less expensive L-glycerol-3-phosphate or DL-glycerol-3-phosphate (Scheme 3) [39]. Such a one-pot multi-enzyme approach represents a cost-effective non

• conversion potential [52]. The production yield could reach above 60% in the presence of glycerol [52] which may be responsible for NAD+/NADH regeneration. Large-scale preparation of L-tagatose has not been extensively studied yet due to elaborate routes or expensive starting materials. In our lab, the

• -talitol catalyzed by a halotolerant yeast strain Candida famata R28 could be significantly increased in the presence of various carbohydrates such as erythritol, D-sorbitol, ribitol and glycerol in the reaction mixture [100]. The faster consumption of the substrate could be explained by the in situ NADH

A protecting group-free synthesis of the Colorado potato beetle pheromone

• Zhongtao Wu,
• Manuel Jäger,
• Jeffrey Buter and
• Adriaan J. Minnaard

Beilstein J. Org. Chem. 2013, 9, 2374–2377, doi:10.3762/bjoc.9.273

• the secondary alcohol at C-2. The synthesis by Faraldos runs via epoxidation of fluoronerol, subsequent acetylation of the alcohol and solvolysis. In 2010, Waymouth reported the chemoselective, catalytic oxidation of glycerol to dihydroxyacetone (Scheme 1) using catalytic [(neocuproine)PdOAc]2OTf2 (2

• conclude that the currently obtained 86% ee suffices. (S)-1,3-dihydroxy-3,7-dimethyl-6-octen-2-one (1). Selective oxidation of glycerol [15] and methyl α-D-glucopyranoside. Approach of synthesis of (S)-1. Synthesis of (S)-1 from geraniol. Reagents and conditions: a) D-(−)-diisopropyl tartrate, Ti(OiPr)4

Gold-catalyzed glycosidation for the synthesis of trisaccharides by applying the armed–disarmed strategy

• Abhijeet K. Kayastha and
• Srinivas Hotha

Beilstein J. Org. Chem. 2013, 9, 2147–2155, doi:10.3762/bjoc.9.252

• mannoside 9 (9%) and lactol 10 (6%), which indicated the hydrolysis of the primary benzyl ether. The gold-catalyzed hydrolysis of benzyl ethers was not observed in the case of non-carbohydrate benzyl ether 11 (Scheme 3). For example, per-O-benzylated glycerol 11 did not show any benzyl deprotection, whereas

• the more acid-sensitive p-methoxybenzyl derivative 12 underwent deprotection of the p-methoxybenzyl moiety to give alcohol 13 with 88% yield. The deprotection of the p-methoxybenzyl moiety can be utilized for the one-pot synthesis of glycerol mannosides from mannosyl donor 1 and compound 12 in 67

• hydrolysis and synthesis of a glycerol mannoside. Armed–disarmed effect in Ech-glycosides during gold-catalyzed reactions. Gold-catalyzed glycosidation at ambient temperature for the synthesis of trimannoside 25. Gold-catalyzed glycosidation at ambient temperature for the synthesis of higher saccharides

1-n-Butyl-3-methylimidazolium-2-carboxylate: a versatile precatalyst for the ring-opening polymerization of ε-caprolactone and rac-lactide under solvent-free conditions

• Astrid Hoppe,
• Faten Sadaka,
• Claire-Hélène Brachais,
• Gilles Boni,
• Jean-Pierre Couvercelle and
• Laurent Plasseraud

Beilstein J. Org. Chem. 2013, 9, 647–654, doi:10.3762/bjoc.9.73

• of ε-caprolactone (ε-CL) and rac-lactide (rac-LA) under solvent-free conditions and using 1-n-butyl-3-methylimidazolium-2-carboxylate (BMIM-2-CO2) as precatalyst is described. Linear and star-branched polyesters were synthesized by successive use of benzyl alcohol, ethylene glycol, glycerol and

• carbon dioxide transfer in the formation of ketoacetates [46][47] and carboxylation of epoxides [48]. Some of us have recently reported a green application of BMIM-2-CO2, highlighting its efficiency for the conversion of raw glycerol to glycerol carbonate by transesterification [49]. More recently, this

• precatalyst. Results and Discussion Two solvent-free polymerization procedures were developed in this study, named methods A and B (Scheme 1). Four initiator alcohols, with an increasing number of OH functions, were successively used: benzyl alcohol (1), ethylene glycol (2), glycerol (3) or pentaerythritol (4

Multivalent display of the antimicrobial peptides BP100 and BP143

• Imma Güell,
• Rafael Ferre,
• Kasper K. Sørensen,
• Esther Badosa,
• Iteng Ng-Choi,
• Emilio Montesinos,
• Eduard Bardají,
• Lidia Feliu,
• Knud J. Jensen and
• Marta Planas

Beilstein J. Org. Chem. 2012, 8, 2106–2117, doi:10.3762/bjoc.8.237

• , Staphylococcus aureus subsp. aureus ATCC 9144 and Salmonella enterica subsp. enterica LT2 ATCC 15277. All bacteria were stored in Luria Bertani (LB) broth except for L. monocytogenes, which was stored in Brain Heart Infusion (BHI) broth (Oxoid, Hampshire, United Kingdom) supplemented with glycerol (20%) and

Design of a novel tryptophan-rich membrane-active antimicrobial peptide from the membrane-proximal region of the HIV glycoprotein, gp41

• Evan F. Haney,
• Leonard T. Nguyen,
• David J. Schibli and
• Hans J. Vogel

Beilstein J. Org. Chem. 2012, 8, 1172–1184, doi:10.3762/bjoc.8.130

• not disrupt bilayer organization in neutral liposomes to the same extent as gp41w or gp41w-4R (Figure 4C). Differential scanning calorimetry The gp41w derivatives were added to 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (DPPG) lipid

• coefficients obtained from Protparam on the EXPASY web server [37]. Powdered dodecylphosphocholine (DPC) and stock chloroform solutions of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (DPPG), egg-derived L-α-phosphatidylcholine (ePC), egg-derived L

Partial thioamide scan on the lipopeptaibiotic trichogin GA IV. Effects on folding and bioactivity

• Marta De Zotti,
• Barbara Biondi,
• Cristina Peggion,
• Matteo De Poli,
• Haleh Fathi,
• Simona Oancea,
• Claudio Toniolo and
• Fernando Formaggio

Beilstein J. Org. Chem. 2012, 8, 1161–1171, doi:10.3762/bjoc.8.129

• -dioleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (DOPG) model membrane was exploited. The extent of permeation induced by the three analogues is similar, although 30–40% lower than that of the parent peptaibiotic. The antimicrobial activities were assessed on a large set of Gram-positive and Gram-negative

Unprecedented deoxygenation at C-7 of the ansamitocin core during mutasynthetic biotransformations

• Tobias Knobloch,
• Gerald Dräger,
• Wera Collisi,
• Florenz Sasse and
• Andreas Kirschning

Beilstein J. Org. Chem. 2012, 8, 861–869, doi:10.3762/bjoc.8.96

• , HGF059, Δasm12/21) were stored as spore suspensions in 40% (v/v) glycerol/water at −80 °C, and used for the inoculation of YMG agar plates. Following incubation of the plates for 4 d at 30 °C, 5–8 well-sporulated colonies were transferred to a 1.5 mL tube charged with 1 mL of sterile distilled water and

Chemo-enzymatic modification of poly-N-acetyllactosamine (LacNAc) oligomers and N,N-diacetyllactosamine (LacDiNAc) based on galactose oxidase treatment

• Christiane E. Kupper,
• Ruben R. Rosencrantz,
• Birgit Henßen,
• Helena Pelantová,
• Stephan Thönes,
• Anna Drozdová,
• Vladimir Křen and
• Lothar Elling

Beilstein J. Org. Chem. 2012, 8, 712–725, doi:10.3762/bjoc.8.80

• -Boc (2) was synthesised as described previously with some modifications [11]. To increase enzyme stability after purification, the buffer was exchanged to storage buffer (100 mM MOPS, 25 mM KCl, pH 6.8) and 20% glycerol was added to reduce protein precipitation. To reach an improved conversion of the

• change of the fermentation temperature to 25 °C was followed by the addition of isopropyl β-D-thiogalactopyranoside (IPTG) yielding a concentration of 1 mM. Additionally a feed (approx. 0.1 mL/min) of 50% (v/v) glycerol in water was applied. Cultivation was terminated 2 h after IPTG addition, yielding 60

An easy α-glycosylation methodology for the synthesis and stereochemistry of mycoplasma α-glycolipid antigens

• Yoshihiro Nishida,
• Yuko Shingu,
• Yuan Mengfei,
• Kazuo Fukuda,
• Hirofumi Dohi,
• Sachie Matsuda and
• Kazuhiro Matsuda

Beilstein J. Org. Chem. 2012, 8, 629–639, doi:10.3762/bjoc.8.70

• one-pot α-glycosylation method was effectively applied. The synthetic GGPL-I isomers were characterized with 1H NMR spectroscopy to determine the equilibrium among the three conformers (gg, gt, tg) at the acyclic glycerol moiety. The natural GGPL-I isomer was found to prefer gt (54%) and gg (39

• and characterized by other groups [11][12][13][14]. Absolute chemical structures of GGPL-I [15] and GGPL–III [16] have already been established by chemical syntheses of stereoisomers; these α-glycolipids have a common chemical backbone of 3-O-(α-D-glucopyranosyl)-sn-glycerol carrying phosphocholine at

• the sugar primary (6-OH) position. The fatty acids at the glycerol moiety are saturated, namely palmitic acid (C16:0) and stearic acid (C18:0). GGPL-I has a structural feature analogous to 1,2-di-O-palmitoyl phosphatidylcholine (DPPC) as a ubiquitous cell membrane phospholipid. Apparently, GGPLs are

Mutational analysis of a phenazine biosynthetic gene cluster in Streptomyces anulatus 9663

• Orwah Saleh,
• Katrin Flinspach,
• Lucia Westrich,
• Andreas Kulik,
• Bertolt Gust,
• Hans-Peter Fiedler and
• Lutz Heide

Beilstein J. Org. Chem. 2012, 8, 501–513, doi:10.3762/bjoc.8.57

• selection of recombinant strains. Chemicals Kanamycin and carbenicillin were purchased from Genaxxon BioSciences GmbH (Biberach, Germany) and phenazine 1-carboxylic acid was from InFormatik. IPTG, Tris, NaCl, glycerol, dithiothreitol, MgCl2, formic acid, sodium dodecyl sulfate, polyacrylamide, and EDTA were

• a further 10 h at 20 °C and harvested. Then, 30 mL of lysis buffer (50 mM Tris-HCl, pH 8.0, 1 M NaCl, 10% glycerol, 10 mM β-mercaptoethanol, 20 mM imidazole, 0.5 mg·mL−1 lysozyme, 0.5 mM phenylmethylsulfonyl fluoride) was added to the pellet (40 g). After being stirred at 4 °C for 30 min, cells were

• Tris-HCl, pH 8.0, 1 M NaCl, 10% glycerol, 10 mM β-mercaptoethanol) for elution. Subsequently, a buffer exchange was carried out by PD10 columns (Amersham Biosciences), which were eluted with 50 mM Tris-HCl, pH 8.0, 1 M NaCl, 10% glycerol, and 2 mM 1,4-dithiothreitol. Approximately 30 mg of purified

The volatiles of pathogenic and nonpathogenic mycobacteria and related bacteria

• Thorben Nawrath,
• Georgies F. Mgode,
• Bart Weetjens,
• Stefan H. E. Kaufmann and
• Stefan Schulz

Beilstein J. Org. Chem. 2012, 8, 290–299, doi:10.3762/bjoc.8.31

• (without glycerol) were washed in order to remove traces of ingredients from the stock-culture medium (7H9). Washing was done three times by mixing the culture (3 mL) with phosphate-buffered saline (PBS; 10 mL) and centrifuging at 4000 rpm for 10 min. Supernatants were decanted and PBS (10 mL) was added to

Biocatalytic hydroxylation of n-butane with in situ cofactor regeneration at low temperature and under normal pressure

• Svenja Staudt,
• Christina A. Müller,
• Jan Marienhagen,
• Christian Böing,
• Stefan Buchholz,
• Ulrich Schwaneberg and
• Harald Gröger

Beilstein J. Org. Chem. 2012, 8, 186–191, doi:10.3762/bjoc.8.20

• order to make sure that this result was not in fact due to a loss of activity of the glucose dehydrogenase from Bacillus sp. at low temperatures, the activity of this enzyme was determined at −10 °C (40 vol % of glycerol) and at −5 °C (30 vol % of glycerol). In this study, the glucose dehydrogenase