Chemical and biosynthetic potential of Penicillium shentong XL-F41

• Ran Zou,
• Xin Li,
• Xiaochen Chen,
• Yue-Wei Guo and
• Baofu Xu

Beilstein J. Org. Chem. 2024, 20, 597–606, doi:10.3762/bjoc.20.52

• , such as medium-chain alcohol dehydrogenase (CpDCS), esterase (CpDCE), P450 and O-methyltransferase (CpOMT1) (Figure S37). Through genome excavation and analysis of Penicillium shentong XL-F41, a significant difference was discovered between the key enzymes involved in the formation of product compound

Synthesis of sulfur karrikin bioisosteres as potential neuroprotectives

• Martin Pošta,
• Václav Zima,
• Lenka Poštová Slavětínská,
• Marika Matoušová and
• Petr Beier

Beilstein J. Org. Chem. 2022, 18, 549–554, doi:10.3762/bjoc.18.57

• °C), 60 min. Inhibition of acetylcholine esterase by the synthesized analogues. Supporting Information Supporting Information File 210: Experimental part, compound characterization and copies of NMR spectra. Funding Financial support from the Czech Science Foundation (20-11571S) and Academy of

Synthetic strategies toward 1,3-oxathiolane nucleoside analogues

• Umesh P. Aher,
• Dhananjai Srivastava,
• Girij P. Singh and
• Jayashree B. S

Beilstein J. Org. Chem. 2021, 17, 2680–2715, doi:10.3762/bjoc.17.182

• manner was reported by Chu et al. [22]. Choi et al. [23] produced the 5-fluoro-substituted analogue of a 1,3-oxathiolane nucleoside as a racemic mixture, and the enantiomers were separated using pig liver esterase (PLE) enzyme, which resulted in 5’-butyroyl ester derivatives. They further explained the

Kinetics of enzyme-catalysed desymmetrisation of prochiral substrates: product enantiomeric excess is not always constant

• Peter J. Halling

Beilstein J. Org. Chem. 2021, 17, 873–884, doi:10.3762/bjoc.17.73

• -reductases. The reductant (usually NADH or NADPH) has to bind first to the enzyme, followed by the prochiral ketone in the second step. The chiral products are then released before the oxidised co-product. “Ping-pong, second”. Followed by most transaminases and lipase or esterase-catalysed acylation of

• prochiral diols. The enzyme reacts with an amino or acyl donor, releasing a first co-product, to give an aminated or acylated enzyme intermediate. This then reacts with the prochiral ketone or diol to generate the chiral products. “Ping-pong, first”. Followed in most lipase or esterase hydrolyses of

• , both”. Followed in most lipase or esterase reactions of prochiral diacids: either hydrolysis of their esters, or esterification of the free acids. The enzyme reacts enantiospecifically with the ester or acid. But now the acyl enzyme can be in either stereoisomeric form, so the kinetics are different

Regioselective chemoenzymatic syntheses of ferulate conjugates as chromogenic substrates for feruloyl esterases

• Olga Gherbovet,
• Fernando Ferreira,
• Apolline Clément,
• Mélanie Ragon,
• Julien Durand,
• Sophie Bozonnet,
• Michael J. O'Donohue and
• Régis Fauré

Beilstein J. Org. Chem. 2021, 17, 325–333, doi:10.3762/bjoc.17.30

• regioselective functionalization of 4-nitrocatechol and enzymatic transferuloylation. The use of this strategy to characterize type A feruloyl esterase from Aspergillus niger reveals the advantages of this substrate for the characterizations of feruloyl esterases. Keywords: esterase; feruloylated conjugates

A chemoenzymatic synthesis of ceramide trafficking inhibitor HPA-12

• Seema V. Kanojia,
• Sucheta Chatterjee,
• Subrata Chattopadhyay and
• Dibakar Goswami

Beilstein J. Org. Chem. 2019, 15, 490–496, doi:10.3762/bjoc.15.42

• chicken liver esterase proceeded with modest enantioselectivity [41][42]. Rhizopus arrhizus-mediated hydrolysis of the acetate furnished the enantiomerically pure alcohol (99% ee), however, the enantiomeric excess (ee) of the antipode acetate was very poor (5–9%) [43]. On the other hand, the Amano PS

Nanoreactors for green catalysis

• M. Teresa De Martino,
• Loai K. E. A. Abdelmohsen,
• Floris P. J. T. Rutjes and
• Jan C. M. van Hest

Beilstein J. Org. Chem. 2018, 14, 716–733, doi:10.3762/bjoc.14.61

• green catalysis. Peptide dendrimers including aspartate, histidine and serine were utilized by Reymond et al. as catalytic esterase triad. Using fluorogenic 8-acyloxypyrene-1,3,6-trisulfonates as substrate (Figure 7) at the pH optimum of 5.5, triads’ activity was successfully demonstrated [107]. A

• embedded in the bilayer. Reprinted with permission from [21]. Copyright 2007 American Chemical Society. Representation of DSN-G0. Reprinted with permission from [100]. The multivalent esterase dendrimer 5 catalyzes the hydrolysis of 8-acyloxypyrene 1,3,6-trisulfonates 6a–c. Reprinted with permission from

Stimuli-responsive oligonucleotides in prodrug-based approaches for gene silencing

• Françoise Debart,
• Christelle Dupouy and
• Jean-Jacques Vasseur

Beilstein J. Org. Chem. 2018, 14, 436–469, doi:10.3762/bjoc.14.32

• due to the conversion of TBANB into TBA. The modulation of the secondary structure transition of an ON in a reduction-responsive manner appears to be beneficial to understand biomolecule behavior and biological phenomena. Esterase-responsive ONs Modifications at the internucleotide linkage: The use of

• and particularly focused on esterase-responsive modified-phosphate ONs [32]. The most studied masking groups have been the methyl-SATE (S-acetylthioethyl) and tert-butyl SATE (S-pivaloylthioethyl) developed by Imbach (Scheme 8A) [29], whereas S-acyloxymethyl groups were studied by Agrawal (Scheme 8B

• liver esterase, but the accumulation of negative charge slowed down the enzymatic hydrolysis. These preliminary data did not provoke further development of such an approach. Unfortunately, despite many strategies, all attempts to synthesize DNA ONs with SATE-phosphotriesters resulted in poor synthetic

A mechanochemical approach to access the proline–proline diketopiperazine framework

• Nicolas Pétry,
• Hafid Benakki,
• Eric Clot,
• Pascal Retailleau,
• Farhate Guenoun,
• Fatima Asserar,
• Chakib Sekkat,
• Thomas-Xavier Métro,
• Jean Martinez and
• Frédéric Lamaty

Beilstein J. Org. Chem. 2017, 13, 2169–2178, doi:10.3762/bjoc.13.217

• liver esterase (PLE)-catalyzed enzymatic hydrolysis of meso cis-11 provided selectively the N-protected amino acid 17 as one enantiomer [33][44][45]. Mechanocoupling of 17 with pyrrolidine 12 provided the dipeptide 18 in excellent yield. Removal of the benzyl group by hydrogenation in the presence of Pd

Glycoscience@Synchrotron: Synchrotron radiation applied to structural glycoscience

• Serge Pérez and
• Daniele de Sanctis

Beilstein J. Org. Chem. 2017, 13, 1145–1167, doi:10.3762/bjoc.13.114

• carbohydrate. One class is exemplified by the pectin methyl esterase in which case the carbohydrate plays the role of the “acid”. In another class, the carbohydrate acts as an alcohol, as in acetylated xylan. A classification based on amino acid sequence similarities has been proposed yielding 16 families [41

Evidence for an iterative module in chain elongation on the azalomycin polyketide synthase

• Hui Hong,
• Yuhui Sun,
• Yongjun Zhou,
• Emily Stephens,
• Markiyan Samborskyy and
• Peter F. Leadlay

Beilstein J. Org. Chem. 2016, 12, 2164–2172, doi:10.3762/bjoc.12.206

• the third is the PKS for the β-lactone ebelactone, a potent esterase inhibitor from Streptomyces aburaviensis 2a,b (Figure 1) [30]. These examples are particularly interesting as potential model systems because the chemical outcome of the two successive extensions catalysed by the iterative module is

Biosynthesis of oxygen and nitrogen-containing heterocycles in polyketides

• Franziska Hemmerling and
• Frank Hahn

Beilstein J. Org. Chem. 2016, 12, 1512–1550, doi:10.3762/bjoc.12.148

• participation of the FMO MoxY in a Baeyer–Villiger oxidation, which yields versiconal acetate (104) [93][94]. This is then hydrolysed by a cytosolic esterase (putatively also coded in the aflatoxin gene cluster as estA) to versiconal (105) [95]. The bisfuran moiety of versicolorin B (106), which is crucial for

• -2-one. Concomitant attack of the intermediately formed hydroxylate on the thioester closes the β-lactone and releases salinosporamide A (199) from the assembly line. Ebelactone A. Ebelactone A (201) is an esterase inhibitor of PKS type I origin that is produced by Streptomyces aburaviensis ATCC 31

Azobenzene-based inhibitors of human carbonic anhydrase II

• Leander Simon Runtsch,
• David Michael Barber,
• Peter Mayer,
• Michael Groll,
• Dirk Trauner and
• Johannes Broichhagen

Beilstein J. Org. Chem. 2015, 11, 1129–1135, doi:10.3762/bjoc.11.127

• bicarbonate and a proton (Figure 1a, left) [1]. Despite its native purpose of pH and pressure regulation, its intrinsic esterase activity can be utilized to measure the catalytic activity by hydrolysis of p-nitrophenyl actetate (pNPA) to a phenolate, of which the product appearance can be observed

A new and convenient synthetic way to 2-substituted thieno[2,3-b]indoles

• Roman A. Irgashev,
• Arseny A. Karmatsky,
• Gennady L. Rusinov and
• Valery N. Charushin

Beilstein J. Org. Chem. 2015, 11, 1000–1007, doi:10.3762/bjoc.11.112

• inhibitors of acetylcholine esterase and butyrylcholine esterase [5], compounds of this series exhibit as well anti-tuberculosis [6] and anti-inflammatory activities [7]. Another promising area for the use of thieno[2,3-b]indoles, as electron-rich heteroaromatics, is the design of photo- and electroactive

Electrochemical oxidation of cholesterol

• Jacek W. Morzycki and
• Andrzej Sobkowiak

Beilstein J. Org. Chem. 2015, 11, 392–402, doi:10.3762/bjoc.11.45

• oxidation current. However, cholesterol in blood is mainly present in form of its fatty acid esters. If the total cholesterol amount is needed, the cholesterol esters must be hydrolyzed prior to analysis by the use of cholesterol esterase [51]. A poor stability of the enzymes and an influence of various

• cholesterol oxidase and cholesterol esterase onto thulium oxide [68] have been found as an alternative for biosensors which operate in blood. Non-enzymatic indirect cholesterol detection with electrochemical techniques Non-enzymatic approaches toward cholesterol detection exploiting an electrochemical route

A versatile δ-aminolevulinic acid (ΑLA)-cyclodextrin bimodal conjugate-prodrug for PDT applications with the help of intracellular chemistry

• Chrysie Aggelidou,
• Theodossis A. Theodossiou,
• Antonio Ricardo Gonçalves,
• Mariza Lampropoulou and
• Konstantina Yannakopoulou

Beilstein J. Org. Chem. 2014, 10, 2414–2420, doi:10.3762/bjoc.10.251

• biosynthesis of protoporphyrin IX and subsequently heme. Synthesis of conjugate 2 i) Br2, Ph3P, DMF, 75–80 °C, 93% according to [16]; ii) 2-hydroxyethylamine, 80 °C, 76%, according to [12]; iii) Βr2, MeOH, rt, 41%; iv) NaN3, THF, 25–30 °C, 90%; v) phosphate buffer, pig liver esterase, pH 8, 25–30 °C, 82%; vi

Glycosystems in nanotechnology: Gold glyconanoparticles as carrier for anti-HIV prodrugs

• Fabrizio Chiodo,
• Marco Marradi,
• Javier Calvo,
• Eloisa Yuste and
• Soledad Penadés

Beilstein J. Org. Chem. 2014, 10, 1339–1346, doi:10.3762/bjoc.10.136

• corresponding ester prodrug candidates with a free thiol-ending group fundamental for their gold chemo-adsorption (Figure 1 and Supporting Information File 1). Abacavir (ABC) and lamivudine (3TC) were functionalized at the primary hydroxy groups through an ester bond that will be cleaved by cellular esterase

Synthesis of complex intermediates for the study of a dehydratase from borrelidin biosynthesis

• Frank Hahn,
• Nadine Kandziora,
• Steffen Friedrich and
• Peter F. Leadlay

Beilstein J. Org. Chem. 2014, 10, 634–640, doi:10.3762/bjoc.10.55

• TBS ethers and methyl esters was performed under mildly acidic conditions followed by pig liver esterase-mediated chemoselective hydrolysis. These conditions are compatible with the presence of a coenzyme A or a SNAc thioester, suggesting that they are generally applicable to the synthesis of complex

• polyketide-derived thioesters suited for biosynthesis studies. Keywords: aldol reaction; coenzyme A; natural products; pig liver esterase; polyketide biosynthesis; protection groups; Introduction Borrelidin (1) is a macrolactone polyketide natural product with promising antibacterial, antimalarial

• compatible for SNAc thioesters (Scheme 1). We envisaged the usage of TBS ether for the protection of the secondary hydroxy group and to protect the carboxylic acid as its methyl ester in the precursors 8, 9a, 9b, 10a and 10b. These groups should be cleavable under mildly acidic or esterase-catalyzed

An overview of the synthetic routes to the best selling drugs containing 6-membered heterocycles

• Marcus Baumann and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2013, 9, 2265–2319, doi:10.3762/bjoc.9.265

• . The presence of the readily hydrolysed acyloxyl methyl ester accounts for much of its enhanced potency acting as a rapid response vasodilator. It is reported that both enantiomers undergo esterase-mediated hydrolysis with short half-lifes of around two minutes and possessing similar medical and

Use of 3-[¹⁸F]fluoropropanesulfonyl chloride as a prosthetic agent for the radiolabelling of amines: Investigation of precursor molecules, labelling conditions and enzymatic stability of the corresponding sulfonamides

• Reik Löser,
• Steffen Fischer,
• Achim Hiller,
• Martin Köckerling,
• Uta Funke,
• Aurélie Maisonial,
• Peter Brust and
• Jörg Steinbach

Beilstein J. Org. Chem. 2013, 9, 1002–1011, doi:10.3762/bjoc.9.115

• in liver cells [44]. Beside its esterase activity the enzyme shows also amidase activity towards amides with various acyl chains and plays a prominent role in the hydrolytic metabolism of many drug molecules including radiopharmaceuticals [45][46]. Notably, the amidase activity of carboxylesterase is

• Information File 1) were exposed to pig-liver esterase (PLE), the porcine homologue of carboxylesterase, in buffered aqueous solution. Fluoroacetamide 19 was prepared by reacting 4-fluoroaniline with fluoroacetyl chloride. The activity of the enzyme preparation was verified using the chromogenic standard

Quantification of N-acetylcysteamine activated methylmalonate incorporation into polyketide biosynthesis

• Stephan Klopries,
• Uschi Sundermann and
• Frank Schulz

Beilstein J. Org. Chem. 2013, 9, 664–674, doi:10.3762/bjoc.9.75

• propionate starter unit with six equivalents of methylmalonyl-coenzyme A (MM-CoA). After six rounds of decarboxylative Claisen condensations and varying degrees of reduction of the initially formed β-keto thioesters, the polyketide core of erythromycin is released from the enzyme via a terminal esterase [6

An improved synthesis of a fluorophosphonate–polyethylene glycol–biotin probe and its use against competitive substrates

• Hao Xu,
• Hairat Sabit,
• Gordon L. Amidon and
• H. D. Hollis Showalter

Beilstein J. Org. Chem. 2013, 9, 89–96, doi:10.3762/bjoc.9.12

• that hydrolyzes the ester group of enalapril and oseltamivir. Enalapril and oseltamivir are commercially available prodrugs, which are converted to enalaprilat and oseltamivir carboxylate, respectively, after being absorbed in the intestine. Carboxylesterase [22], a common esterase existing in multiple

Thioester derivatives of the natural product psammaplin A as potent histone deacetylase inhibitors

• Matthias G. J. Baud,
• Thomas Leiser,
• Vanessa Petrucci,
• Mekala Gunaratnam,
• Stephen Neidle,
• Franz-Josef Meyer-Almes and
• Matthew J. Fuchter

Beilstein J. Org. Chem. 2013, 9, 81–88, doi:10.3762/bjoc.9.11

• the source of HDACs, potentially containing esterases, which may have cleaved the thioester during the assay. On the contrary, we observed the same pattern with purified rHDAC1 and purified rHDAC6, which obviously contains no such potential for esterase-driven hydrolysis. Recently, Williams reported

Marilones A–C, phthalides from the sponge-derived fungus Stachylidium sp.

• Celso Almeida,
• Stefan Kehraus,
• Miguel Prudêncio and
• Gabriele M. König

Beilstein J. Org. Chem. 2011, 7, 1636–1642, doi:10.3762/bjoc.7.192

• , papain, porcine cease and acetylcholine esterase) were performed according to Neumann et al. [19]. Compounds were tested for protein kinase inhibition assays (DYRK1A and CDK5) according to Bettayeb et al. [20]. The triglyceride accumulation inhibition in the 3T3-L1 murine adipocytes assay was performed

Oxidative allylic rearrangement of cycloalkenols: Formal total synthesis of enantiomerically pure trisporic acid B

• Silke Dubberke,
• Muhammad Abbas and
• Bernhard Westermann

Beilstein J. Org. Chem. 2011, 7, 421–425, doi:10.3762/bjoc.7.54

• resolution; natural products; oxidative rearrangement; pig liver esterase (PLE); trisporic acid B; Introduction The generation of chiral, non-racemic compounds bearing a stereogenic quaternary carbon centre is of great interest [1][2][3][4][5][6][7][8]. Therefore, much effort has been directed towards the

• synthesis of this stereogenic unit and solutions have been found, e.g., by Christoffers and d’Angelo [9][10][11]. We have already disclosed our results to obtain these products highly enantiomerically enriched by pig liver esterase (PLE) catalyzed saponification of α-substituted β-ketoesters [12][13]. We

• -ketoester 1c, the racemate 1c is resolved by a pig liver esterase (PLE)-catalyzed saponification reaction. As in other cases reported earlier, the racemic β-ketoesters are hydrolyzed with high stereoselectivity allowing the isolation of optically pure esters (–)-1. The corresponding hydrolysis products, the