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Search for "biosynthesis" in Full Text gives 320 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Discovery of unguisin J, a new cyclic peptide from Aspergillus heteromorphus CBS 117.55, and phylogeny-based bioinformatic analysis of UngA NRPS domains
Beilstein J. Org. Chem. 2024, 20, 321–330, doi:10.3762/bjoc.20.32
- of the UngA NRPS were analyzed in an attempt to understand the lack of substrate specificity observed. Keywords: adenylation domain; condensation domain; fungal non-ribosomal peptide synthetase; heptapeptide; unguisin biosynthesis; Introduction Unguisins are a small family of fungal cyclic
- small peptides [3][4][9], however, unguisin A has been shown to bind a series of anions [10]. Recently the biosynthesis of unguisins A and B from Aspergillus violaceofuscus CBS 115571 was reported [5]. A seven module non-ribosomal peptide synthetase (NRPS; UngA) was heterologously expressed in
- , from Aspergillus heteromorphus CBS 117.55. We also perform bioinformatic analysis of the A and C domains of the UngA NRPS enzymes involved in their biosynthesis to try and rationalize the relaxed substrate specificity observed in this family of heptapeptides. Results and Discussion The cultivation of A
Optimizations of lipid II synthesis: an essential glycolipid precursor in bacterial cell wall synthesis and a validated antibiotic target
Beilstein J. Org. Chem. 2024, 20, 220–227, doi:10.3762/bjoc.20.22
- analogues through the incorporation of alternative building blocks at different stages of synthesis. Keywords: chemical glycosylation; lipid II; peptidoglycan; polyprenyls; total synthesis; Introduction Lipid II (Figure 1) is an essential bacterial glycolipid involved in peptidoglycan biosynthesis [1]. It
- is synthesized on the inner leaflet of the cytoplasmic membrane, before translocation to the outer leaflet, where it is then used as the monomeric building block of peptidoglycan biosynthesis. Lipid II is a validated antibiotic target for clinically prescribed antibiotics including vancomycin and
Identification of the p-coumaric acid biosynthetic gene cluster in Kutzneria albida: insights into the diazotization-dependent deamination pathway
Beilstein J. Org. Chem. 2024, 20, 1–11, doi:10.3762/bjoc.20.1
- biosynthesis by heterologous expression of the cma cluster and in vitro enzyme assays using recombinant Cma proteins. The ATP-dependent diazotase CmaA6 catalyzed the diazotization of both 3-aminocoumaric acid and 3-aminoavenalumic acid using nitrous acid in vitro. In addition, the high efficiency of the CmaA6
- reaction enabled us to perform a kinetic analysis of AvaA7, which confirmed that AvaA7 catalyzes the denitrification of 3-diazoavenalumic acid in avenalumic acid biosynthesis. This study deepened our understanding of the highly reducing type II polyketide synthase system as well as the diazotization
- -dependent deamination pathway for the production of avenalumic acid or p-coumaric acid. Keywords: actinomycetes; avenalumic acid; biosynthesis; p-coumaric acid; polyketides; Introduction The genomes of microorganisms possess diverse biosynthetic gene clusters (BGCs) to produce natural products [1]. In
Anion–π catalysis on carbon allotropes
Beilstein J. Org. Chem. 2023, 19, 1881–1894, doi:10.3762/bjoc.19.140
- ][56][57]. Anion–π catalysis on fullerenes has been introduced in 2017 [12]. Fullerene anion–π catalysts were developed with the benchmark reaction introduced two years earlier (Figure 2) [2]. In this reaction, at the beginning of all biosynthesis, finetuned malonic acid half thioesters 4 [58][59][60
- catalysis. Moreover, epoxide opening polyether cyclizations are among the most impressive cascade reactions in nature [71][72][73]. Best known is the hypothetical cascade XII in the biosynthesis of brevetoxin B [74]. It affords eleven fused ethers by violating the Eschenmoser–Dunitz–Baldwin guidelines [75
Sulfur-containing spiroketals from Breynia disticha and evaluations of their anti-inflammatory effect
Beilstein J. Org. Chem. 2023, 19, 1604–1614, doi:10.3762/bjoc.19.117
- the onset of anti-inflammatory action. Conclusion The biosynthesis of breynins with novel skeletons remains poorly understood, especially with respect to the sulfur source. In this study, we isolated a new aglycone, probreynogenin (3), together with a known sesquiterpenoid, phyllaemblic acid (5
Synthesis and biological evaluation of Argemone mexicana-inspired antimicrobials
Beilstein J. Org. Chem. 2023, 19, 1511–1524, doi:10.3762/bjoc.19.108
- often attributed to high binding affinity to DNA, interference with protein biosynthesis, induction of membrane leakage, and affecting GTPase activity in bacteria cell division [12][13][14][15]. Recent reports have also pointed to inhibition of the ‘filamenting temperature-sensitive mutant Z’ (FtsZ
Unraveling the role of prenyl side-chain interactions in stabilizing the secondary carbocation in the biosynthesis of variexenol B
Beilstein J. Org. Chem. 2023, 19, 1503–1510, doi:10.3762/bjoc.19.107
- completed through bridging from the exomethylene group, and (iii) the annulation from the exomethylene group proceeds in a barrier-free manner. Keywords: biosynthesis; carbocation; cation–π interaction; DFT; terpene; Introduction Terpene/terpenoids are most abundant natural products in nature, more than
- as the C–H–π interaction between the carbocation intermediate and the Phe residue of terpene cyclase in the biosynthesis of sesterfisherol [21], and the intricated rearrangement reaction mechanism promoted by the equilibrium state of the homoallyl cation and the cyclopropylcarbinyl cation in the
- biosynthesis of trichobrasilenol [22], by combined methods of computational and experimental chemistry. Recently, Dickschat et al. reported the synthesis of a novel diterpene compound, variexenol B, using a substrate analogue called iso-GGPP (Scheme 1) [23]. This biosynthetic pathway has two interesting
Functions of enzyme domains in 2-methylisoborneol biosynthesis and enzymatic synthesis of non-natural analogs
Beilstein J. Org. Chem. 2023, 19, 1452–1459, doi:10.3762/bjoc.19.104
- Binbin Gu Lin-Fu Liang Jeroen S. Dickschat Kekulé-Institute of Organic Chemistry and Biochemistry, University of Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn, Germany 10.3762/bjoc.19.104 Abstract Two aspects of the biosynthesis of the non-canonical terpene synthase for 2-methylisoborneol have been
- of the 2-methylisoborneol synthase was investigated through enzyme incubations with several substrate analogs, giving access to two C12 monoterpenoids. Implications on the stereochemical course of the terpene cyclisation by 2-methylisoborneol synthase are discussed. Keywords: biosynthesis; enzymes
- unpleasant off-flavour [19][20]. The biosynthesis of 1 has been extensively studied. The initial hypothesis that 1 could be a degraded sesquiterpene [3] was not confirmed through isotopic labelling experiments that rather pointed to a methylated monoterpene [10][21]. Based on these experiments a biosynthetic
Functional characterisation of twelve terpene synthases from actinobacteria
Beilstein J. Org. Chem. 2023, 19, 1386–1398, doi:10.3762/bjoc.19.100
- ; biosynthesis; enzymes; NMR spectroscopy; terpenes; Introduction Terpene synthases are remarkable enzymes that can convert acyclic and achiral oligoprenyl pyrophosphates into terpene hydrocarbons or alcohols of high structural complexity. These enzymatic reactions are initiated by ionisation of the substrate
- recently identified in which sesquiterpenes from bacteria showed an enantiomeric relationship to plant compounds [36]. The enzyme from K. kofuensis represents the first terpene synthase for the biosynthesis of 10 and was thus identified as Kutzneria kofuensis (+)-δ-Cadinol Synthase (KkdCS). A few closely
- ). The optical rotation of [α]D25 = –9.4 (c 0.64, CH2Cl2) pointed to the same enantiomer as in the plant Viguiera oblongifolia ([α]D24 = –8 (c 0.4, CHCl3)) [43]. A (−)-amorpha-4,11-diene synthase (ADS) is also known from Artemisia annua and catalyses the first committed step in the biosynthesis of
Synthesis of ether lipids: natural compounds and analogues
Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96
- distribution is heterogeneous with abundant amount (up to 50% of the phosphoethanolamine based lipids) in central nervous system (mainly as PE-plasmalogen), in skeletal muscle, heart, kidney and lungs [13]. At a cellular scale, the biosynthesis of ELs is initiated in peroxisome and maturation is completed in
- ) KO mouse which is a mouse model that stop the biosynthesis of ELs [22]. In that case, a reduction of the levels of various neurotransmitters were evidenced likely due to an alteration of the transport efficacy assumed by the synaptic vesicles. The phenotype of these KO mouse shows impaired social
Cyanothioacetamides as a synthetic platform for the synthesis of aminopyrazole derivatives
Beilstein J. Org. Chem. 2023, 19, 1191–1197, doi:10.3762/bjoc.19.87
- the biosynthesis of fatty acids in plants, which leads to herbicidal activity [9]. Pyraclonil is used as a protoporphyrinogen oxidase inhibitor for weed control. Such inhibitors not only block the production of chlorophyll and gem in plant pests, but also lead to the formation of highly reactive
Photoredox catalysis enabling decarboxylative radical cyclization of γ,γ-dimethylallyltryptophan (DMAT) derivatives: formal synthesis of 6,7-secoagroclavine
Beilstein J. Org. Chem. 2023, 19, 918–927, doi:10.3762/bjoc.19.70
- -dimethylallyltryptophan (DMAT) derivatives containing unactivated alkene moieties has been developed, providing green and efficient access to various six-, seven-, and eight-membered ring 3,4-fused tricyclic indoles. This type of cyclization, which was hitherto very difficult to comprehend in ergot biosynthesis and to
- : 1) it functions as the central intermediate in the biosynthetic pathways leading to numerous prenylated indole alkaloids, such as ergot alkaloids in normal biosynthesis and clavicipitic acid in derailment biosynthesis [68][69][70][71]; and 2) the mechanism of the fundamental central C-ring formation
Intermediates and shunt products of massiliachelin biosynthesis in Massilia sp. NR 4-1
Beilstein J. Org. Chem. 2023, 19, 909–917, doi:10.3762/bjoc.19.69
- underlie discrete regulation mechanisms, which explains their context-dependent production [27]. The examples of P. aeruginosa and B. anthracis suggest that siderophore biosynthesis sometimes requires specific triggers beyond iron deficiency, which may not be met under laboratory conditions. The six
- ] and the photoxenobactins [32]. A unifying theme in the biosynthesis of these natural products is the use of a thiotemplate-based assembly strategy [33]. The molecular building blocks that are needed for the biosynthesis are covalently bound via thioester bonds to multi-domain enzymes. The domains
- fulfill specific functions, ranging from the selection and linkage of building blocks to their chemical modification. A plausible scenario for the formation of compounds 1–6 involves the enzymatic machinery for massiliachelin biosynthesis, namely the protein RS02200 [18]. According to our proposal (Figure
Total synthesis: an enabling science
Beilstein J. Org. Chem. 2023, 19, 474–476, doi:10.3762/bjoc.19.36
- synthetic methodology developments and to natural product isolation or biosynthesis. Thus, thematic issues dealing with total synthesis in the Beilstein Journal of Organic Chemistry have naturally been published in these fields, such as "Transition-metal and organocatalysis in natural product synthesis
- " (edited by D. Chen and D. Ma) [1] or "Natural products in synthesis and biosynthesis" (edited twice by J. Dickschat) [2][3]. Previously, the early thematic issue "Indolizidines and quinolizidines: natural products and beyond" (edited by J. P. Michael) from 2007 [4] displayed some of the very first total
Combretastatins D series and analogues: from isolation, synthetic challenges and biological activities
Beilstein J. Org. Chem. 2023, 19, 399–427, doi:10.3762/bjoc.19.31
- called cyclic diaryl ether heptanoids (DAEH). This review is intended to highlight the structure elucidation, biosynthesis, and biological activity of these compounds as well as the use of different strategies for their synthesis. Keywords: combretastatin D; corniculatolide; isocorniculatolide
Strategies to access the [5-8] bicyclic core encountered in the sesquiterpene, diterpene and sesterterpene series
Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23
Germacrene B – a central intermediate in sesquiterpene biosynthesis
Beilstein J. Org. Chem. 2023, 19, 186–203, doi:10.3762/bjoc.19.18
- Houchao Xu Jeroen S. Dickschat Kekulé-Institute of Organic Chemistry and Biochemistry, University of Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn, Germany 10.3762/bjoc.19.18 Abstract Germacranes are important intermediates in the biosynthesis of eudesmane and guaiane sesquiterpenes. After their
- references. Keywords: biosynthesis; configuration determination; germacrene B; structure elucidation; terpenes; Introduction Terpenoids constitute the largest class of natural products with ca. 100,000 known compounds. Biosynthetically, all terpenoids are derived from only a few acyclic precursors
- combined computational and experimental approach that in this enzyme the main chain carbonyl oxygen of Gly182 near the helix G kink and an active site water are involved in the deprotonation–reprotonation sequence in the biosynthesis of 10 (Scheme 8B) [69]. γ-Selinene (10) has been synthesised from ketone
Identification and determination of the absolute configuration of amorph-4-en-10β-ol, a cadinol-type sesquiterpene from the scent glands of the African reed frog Hyperolius cinnamomeoventris
Beilstein J. Org. Chem. 2023, 19, 167–175, doi:10.3762/bjoc.19.16
- Information File 1). The same enantiomer was isolated from the wood oil of Cryptomeria japonica [17]. Therefore, the enantiomer R-14 from the frogs is different to the plant compound. This finding may point to a biosynthesis of 14 by the frogs themselves or by associated microorganisms, although uptake from
- synthesis and characterization showed that this compound is the opposite enantiomer of 14 known from plants. This may indicate biosynthesis in the frog, but more work has to be performed to establish this. Furthermore, a short diversity-oriented synthesis based on the work of Taber and Gunn [13] enabled
Revisiting the bromination of 3β-hydroxycholest-5-ene with CBr4/PPh3 and the subsequent azidolysis of the resulting bromide, disparity in stereochemical behavior
Beilstein J. Org. Chem. 2023, 19, 91–99, doi:10.3762/bjoc.19.9
- acts as fluidity buffer, permeability switch, and consequently in cell signaling pathways. Physiologically, cholesterol is the substrate for the biosynthesis of steroidal hormones, vitamin D and bile acids [1][2]. Although cholesterol can adopt 256 stereoisomeric structures, biological significances
- cholesterol biosynthesis (statins). However, the side effects of these drugs are controversial. Therefore, synthetic cholesterol derivatives came into focus for recent applications in chemical biology and materials science [6]. The advances have been summarized in comprehensive reviews [7][8]. In previous
Digyalipopeptide A, an antiparasitic cyclic peptide from the Ghanaian Bacillus sp. strain DE2B
Beilstein J. Org. Chem. 2022, 18, 1763–1771, doi:10.3762/bjoc.18.185
- insertion of different amino acids, homologous extension and linear, isopropyl or isobutyl termination of fatty acid chains. Therefore, the biosynthesis of compound 1 is speculated to occur via a similar pathway like the surfactins, which is known to be modulated by four enzyme subunits SrfAA, SrfAB, SrfAC
- DMSO-d6, HRESIMSMS sequence tagging data with GNPS molecular networking and the advanced Marfey’s test. We proposed that the biosynthesis of compound 1 is similar to that of other surfactin-like lipopeptides previously reported in the literature. We found compound 1 to possess remarkable antiparasitic
Total synthesis of grayanane natural products
Beilstein J. Org. Chem. 2022, 18, 1707–1719, doi:10.3762/bjoc.18.181
- known to date. Thus, we anticipate that in the future, organic chemists will keep focusing on highly enantioselective, efficient and flexible synthetic strategies towards grayanane natural products. General structure of grayanane natural products. Grayanane biosynthesis. Matsumoto’s relay approach
Navigating and expanding the roadmap of natural product genome mining tools
Beilstein J. Org. Chem. 2022, 18, 1656–1671, doi:10.3762/bjoc.18.178
- combination of all genome mining approaches will pave the way towards a more comprehensive understanding of the full biosynthetic repertoire encoded in microbial genome sequences. Keywords: genome mining; natural product biosynthesis; non-canonical pathways; PKS; NRPS; RiPP; Introduction In 2002, the genome
- bioinformatic analysis of (meta-)genomes to identify gene clusters involved in the biosynthesis of NPs [3]. NPs have been shown to act as signaling metabolites (e.g., acylhomoserine lactones (1) [6]), siderophores (e.g., pyoverdines (2) [7]), virulence factors (e.g., malleicyprol (3) [8][9][10]), toxins (e.g
- biosynthetic concepts. NP biosynthesis follows two fundamentally different principles: NPs can either be produced in an assembly line-like fashion (Figure 2A) or by discrete, multi-enzymatic assemblies (Figure 2B). Discrete, multi-enzymatic assemblies utilize monofunctional enzymes for the consecutive build-up
Solid-phase total synthesis and structural confirmation of antimicrobial longicatenamide A
Beilstein J. Org. Chem. 2022, 18, 1560–1566, doi:10.3762/bjoc.18.166
- products. For example, the mycolic acid-containing bacterium Tsukamurella pulmonis TP-B0596 can influence the biosynthesis of cryptic natural products [3]. Additionally, we have developed several highly sensitive labeling reagents to detect and identify scarce and cryptic natural products [4]. Integrating
- ] and provides insights into the biosynthesis pathways of these peptides [14]. However, the biosynthetic gene clusters of compounds 1–4 remain unidentified. Therefore, the least sterically hindered amine, namely the amino group of glycine, was selected as a nucleophile of the cyclization reaction in
Characterization of a new fusicoccane-type diterpene synthase and an associated P450 enzyme
Beilstein J. Org. Chem. 2022, 18, 1396–1402, doi:10.3762/bjoc.18.144
- become a promising strategy for targeted discovery of natural products [10][11][12], which can also provide enzymatic tools toward combinatorial biosynthesis [13][14]. As terpene synthases play a fundamental role in constructing molecular skeletons, great efforts have been devoted to mining novel
- analyze the function of TadA, we introduced tadA into the quadruple auxotrophic host Aspergillus oryzae NSAR1 (niaD−, sC−, ∆argB, adeA−) (Supporting Information 1, Tables S1 and S2) [26], which has been widely used for biosynthesis of fungi-derived natural products due to its genetic tractability [27
- cytotoxic FC-type diterpenoid isolated from T. purpurogenus PP-414 [7]. It will be important to elucidate the biosynthetic pathway of roussoellol C, providing enzymatic tools for expanding the chemical diversity of talaro-7,13-diene related FC-type diterpenoids via combinational biosynthesis [14
Synthesis of C6-modified mannose 1-phosphates and evaluation of derived sugar nucleotides against GDP-mannose dehydrogenase
Beilstein J. Org. Chem. 2022, 18, 1379–1384, doi:10.3762/bjoc.18.142
- pathogen in these cases is mucoid Pseudomonas aeruginosa. Such infections are characterised by overproduction of the exopolysaccharide alginate. We present herein the design and chemoenzymatic synthesis of sugar nucleotide tools to probe a critical enzyme within alginate biosynthesis, GDP-mannose
- , starting from fructose 6-phosphate and its synthesis ultimately arrives at the limiting step in alginate precursor biosynthesis, the action of GDP-mannose dehydrogenase (GMD), which oxidises GDP-mannose 1 to 5 (Figure 1a). GMD oxidation is suggested to have four discrete steps, first oxidising C6 to an
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