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Search for "terpene" in Full Text gives 85 result(s) in Beilstein Journal of Organic Chemistry.
The enzyme mechanism of patchoulol synthase
Beilstein J. Org. Chem. 2022, 18, 13–24, doi:10.3762/bjoc.18.2
- compound 3 and several biogenetically related terpene hydrocarbons including α-patchoulene (4), β-patchoulene (5), α-bulnesene (6) and α-guaiene (7) (Figure 1) [7]. The enzyme was subsequently made available by cDNA gene cloning, revealing germacrene A (8), α-humulene (9), (E)-β-caryophyllene (10
- contradictory. For this reason, we have reinvestigated the enzyme mechanism of PTS in isotopic labelling experiments through methods recently developed in our laboratory that make use of 13C and 2H-substituted terpene precursors, and by DFT calculations. The general strategy in these experiments is to use
- terpene biosynthesis through neutral intermediates, and more specifically another example of sesquiterpene biosynthesis through the widespread biosynthetic intermediate germacrene A [11]. Initially assigned structures for patchoulol by Treibs (1) and by Büchi (2). Structures of patchoulol (3) and side
Targeting active site residues and structural anchoring positions in terpene synthases
Beilstein J. Org. Chem. 2021, 17, 2441–2449, doi:10.3762/bjoc.17.161
- , turning SmTS1 from a sesterterpene into a diterpene synthase. This article gives rational explanations for these findings that may generally allow for protein engineering of other terpene synthases to improve their catalytic efficiency or to change their functions. Keywords: biosynthesis; enzyme
- (GFPP, C25) for sesterterpene biosynthesis. Type I terpene synthases (TPSs) activate these acyclic molecules by the abstraction of diphosphate to produce a reactive allyl cation that can initiate a cascade reaction through typical carbocation chemistry, including cyclisation reactions by intramolecular
- attack of an olefinic double bond to the cationic centre Wagner–Meerwein rearrangements, and proton or hydride migrations [2]. These multistep cascade reactions ultimately result in terpene hydrocarbons that are often (poly)cyclic and contain several stereogenic centres [3][4]. In some cases, water is
Halides as versatile anions in asymmetric anion-binding organocatalysis
Beilstein J. Org. Chem. 2021, 17, 2270–2286, doi:10.3762/bjoc.17.145
- transformations such as cyclizations or nucleophilic additions. Inspired by cationic terpene-type cyclization cascades, Jacobsen’s group turned their attention to the structure and properties of the chiral part of thiourea catalysts by introducing extended π-groups. A series of thiourea catalysts 53–55 with
Natural products in the predatory defence of the filamentous fungal pathogen Aspergillus fumigatus
Beilstein J. Org. Chem. 2021, 17, 1814–1827, doi:10.3762/bjoc.17.124
- decatetraenedioic acid connected via an ester bond. There is also a methoxy group, an epoxide and a terpene derived aliphatic chain that contains another epoxide, linked to cyclohexane. These unstable di-epoxides are responsible for the biological activity of fumagillin, which targets the active site of the
Volatile emission and biosynthesis in endophytic fungi colonizing black poplar leaves
Beilstein J. Org. Chem. 2021, 17, 1698–1711, doi:10.3762/bjoc.17.118
- -insect interactions. Keywords: Ascomycota; Cladosporium; Salicaceae; terpene synthases; volatile organic compound (VOC); Introduction Plant volatile organic compounds (VOCs) can mediate plant–insect, plant–microbe, and plant–plant interactions [1][2][3][4]. The constitutive and herbivore-induced
- by the mevalonate pathway in fungi [42]. The condensation of DMAPP with varying numbers of IPP residues results in products of various chain lengths: geranyl diphosphate (GPP, C10), farnesyl diphosphate (FPP, C15), and geranylgeranyl diphosphate (GGPP, C20). Terpene synthases (TPS) then convert the
- precursors GPP, FPP, and GGPP into the different terpene skeletons [42][43][44]. However, our knowledge on terpene synthases of endophytic fungi is scarce, specifically in comparison to the vast knowledge on these enzymes in plants and bacteria [44][45]. Typical monoterpenes like limonene and linalool (5
A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries
Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90
On the mass spectrometric fragmentations of the bacterial sesterterpenes sestermobaraenes A–C
Beilstein J. Org. Chem. 2020, 16, 2807–2819, doi:10.3762/bjoc.16.231
- bacterial sesterterpenes that were recently discovered by us from the actinomycete Streptomyces mobaraensis through a genome mining approach (Figure 1) [1]. All seven compounds are produced by a canonical terpene synthase, representing the first reported sesterterpene synthase of the classical type I from
- initiate a cationic cyclisation cascade, leading to structurally highly complex and usually polycyclic terpenes in just one enzymatic transformation. The initially formed products are non-functionalised terpene hydrocarbons or, if the terminal cationic intermediate of the cyclisation cascade is trapped by
- allows to identify interesting candidate genes coding for terpene synthases for further studies by genome mining. A major difficulty in the GC–MS-based identification of terpenes is associated with the high similarity of the mass spectra of structurally related terpenes. For this reason, the unambiguous
3-Acetoxy-fatty acid isoprenyl esters from androconia of the ithomiine butterfly Ithomia salapia
Beilstein J. Org. Chem. 2020, 16, 2776–2787, doi:10.3762/bjoc.16.228
- , acylated isoprenyl esters of fatty acids, is described, representing a combination of fatty acid and terpene biosynthesis. We also reveal small but reproducible differences between the two subspecies that could potentially be involved in species recognition and reproductive isolation. Results Extracts from
- originate from the terpene building block 3-methyl-3-butenyl (isoprenyl) pyrophosphate. Because isoprenyl pyrophosphate is partly converted to 3-methyl-2-butenyl (prenyl) pyrophosphate during terpene biosynthesis, the presence of prenyl esters could not be excluded. Nevertheless, the two ester types can be
Hierarchically assembled helicates as reaction platform – from stoichiometric Diels–Alder reactions to enamine catalysis
Beilstein J. Org. Chem. 2020, 16, 2338–2345, doi:10.3762/bjoc.16.195
- . The low yield may be attributed to the poor solubility of the helicate. The other terpene [35][36] derived systems Li[Li3(1)3(5)3Ti2] and Li[Li3(1)3(6)3Ti2] showed a different behavior. The (1S,2S,3S,5R)-3-pinanyl-substituted Li[Li3(1)3(5)3Ti2] yielded 46% ee, while the complex bearing a ʟ-(−)-borneyl
Antibacterial scalarane from Doriprismatica stellata nudibranchs (Gastropoda, Nudibranchia), egg ribbons, and their dietary sponge Spongia cf. agaricina (Demospongiae, Dictyoceratida)
Beilstein J. Org. Chem. 2020, 16, 1596–1605, doi:10.3762/bjoc.16.132
- study. Sesterterpenes are a rare terpene class, accounting for less than 2% of all known terpenoids, with only a few reports on their biosynthesis [72][73][74][75][76]. However, their frequent occurrence in marine organisms is striking and sponges are considered as the prime source of these terpenoids
Understanding the role of active site residues in CotB2 catalysis using a cluster model
Beilstein J. Org. Chem. 2020, 16, 50–59, doi:10.3762/bjoc.16.7
- , Dept. of Chemistry, Technical University of Munich (TUM), Lichtenbergstr. 4, 85748 Garching, Germany 10.3762/bjoc.16.7 Abstract Terpene cyclases are responsible for the initial cyclization cascade in the multistep synthesis of a large number of terpenes. CotB2 is a diterpene cyclase from Streptomyces
- cascade can provide important information towards a biosynthetic strategy for cyclooctatin and the biomanufacturing of related terpene structures. Keywords: active site; CotB2 cyclase; diterpene; mechanism; quantum mechanics; Introduction Enzymes catalyze numerous complex biochemical reactions in
- different cellular compartments [1][2]. More specifically, the enigmatic class of terpene cyclases is responsible for converting linear aliphatic oligoprenyl diphosphates into various chemically complex macrocyclic products. The resulting terpene scaffolds and their functionalized terpenoid analogues
Terpenes
Beilstein J. Org. Chem. 2019, 15, 2966–2967, doi:10.3762/bjoc.15.292
- initially formed terpene hydrocarbons can subsequently be modified by enzymatic oxidations that often involve radical chemistry. The non-functionalised hydrocarbons are volatile and often exhibit interesting odour properties [3]. As a consequence, these compounds may act as chemical signals such as
- taxol from Taxus brevifolia that is used to treat breast and other types of solid cancers, while artemisinin from Artemisia annua is used as a cure against malaria [4]. This thematic issue covers all different aspects of terpene chemistry and biochemistry, including compound isolation and structure
Bacterial terpene biosynthesis: challenges and opportunities for pathway engineering
Beilstein J. Org. Chem. 2019, 15, 2889–2906, doi:10.3762/bjoc.15.283
- potential with molecular structure is severely restricted. The canonical terpene biosynthetic pathway uses a single enzyme to form a cyclized hydrocarbon backbone followed by modifications with a suite of tailoring enzymes that can generate dozens of different products from a single backbone. This
- functional promiscuity of terpene biosynthetic pathways renders terpene biosynthesis susceptible to rational pathway engineering using the latest developments in the field of synthetic biology. These engineered pathways will not only facilitate the rational creation of both known and novel terpenoids, their
- development will deepen our understanding of a significant branch of biosynthesis. The biosynthetic insights gained will likely empower a greater degree of engineering proficiency for non-natural terpene biosynthetic pathways and pave the way towards the biotechnological production of high value terpenoids
Emission and biosynthesis of volatile terpenoids from the plasmodial slime mold Physarum polycephalum
Beilstein J. Org. Chem. 2019, 15, 2872–2880, doi:10.3762/bjoc.15.281
- Xinlu Chen Tobias G. Kollner Wangdan Xiong Guo Wei Feng Chen Department of Plant Sciences, University of Tennessee, Knoxville, TN 37996, USA Department of Biochemistry, Max Planck Institute for Chemical Ecology, Hans-Knöll-Strasse 8, D-07745 Jena, Germany 10.3762/bjoc.15.281 Abstract Terpene
- the monoterpene linalool. There were no qualitative differences in terpenoid composition at two stages of young plasmodia. To understand terpene biosynthesis, we analyzed the transcriptome and genome sequences of P. polycephalum and identified four TPS genes designated PpolyTPS1–PpolyTPS4. They share
- relatedness to bacterial TPSs. The biological role of the volatile terpenoids produced by the plasmodia of P. polycephalum is discussed. Keywords: amoebae; evolution; terpene synthases; volatiles; Introduction Volatile organic compounds (VOCs) are used by many living organisms as chemical languages for
Nanangenines: drimane sesquiterpenoids as the dominant metabolite cohort of a novel Australian fungus, Aspergillus nanangensis
Beilstein J. Org. Chem. 2019, 15, 2631–2643, doi:10.3762/bjoc.15.256
- -type sesquiterpenoids from farnesyl diphosphate is proposed to proceed via the protonation-initiated mechanism (class II terpene synthases) [24], which is distinct from the ionisation-initiated mechanism (class I) terpene synthases, where a carbocation is generated by the release of a diphosphate group
- [30]. Therefore, the drimane synthase is likely to be different from the commonly observed sesquiterpene synthase, which belongs to the class I terpene synthases. Recently, the drimane synthase AstC involved in biosynthesis of the astellolides was identified and shown to be a novel member of the
- terpene synthase family, showing similarity to haloacid dehalogenase (HAD)-like hydrolases [21]. Thus, we suspected that a related enzyme may be involved in the biosynthesis of the nanangenines, and used the amino acid sequence of AstC to probe the A. nanangensis genome. We also hypothesised that the acyl
Synthetic terpenoids in the world of fragrances: Iso E Super® is the showcase
Beilstein J. Org. Chem. 2019, 15, 2590–2602, doi:10.3762/bjoc.15.252
- , about 100 natural fragrance ingredients are known, but perfumers have more than 3,000 synthetic molecules at hand of which several examples 60–66 with terpene-like structures are listed in Figure 6. Noteworthy, the fragrance properties of synthetically-derived unnatural compounds commonly mimic those of
- biology will appear on the stage of the world of fragrances [40][41]. Terpene constituents 1–9 found in geranium and bergamot oils and specified odours of individual components. Perfumes are composed of compounds that are perceived immediately (top notes), that form the principal bouquet (heart notes) and
- ), Iso E Super® (33) (1972, odour threshold: 500 ng L−1), timberole (1982, odour threshold: 26 ng L−1) Iso E Super Plus® (34) (1990, odour threshold: 5 pg L−1) and Georgywood® (35, 1996, odour threshold: 15 pg L−1–30 pg L−1) [9][15][33][35][36][37][38]. Branched, terpene-like cyclohexene derivatives
Chiral terpene auxiliaries V: Synthesis of new chiral γ-hydroxyphosphine oxides derived from α-pinene
Beilstein J. Org. Chem. 2019, 15, 2493–2499, doi:10.3762/bjoc.15.242
Current understanding and biotechnological application of the bacterial diterpene synthase CotB2
Beilstein J. Org. Chem. 2019, 15, 2355–2368, doi:10.3762/bjoc.15.228
- mutagenesis have exciting applications for the sustainable production of high value bioactive substances. Keywords: biotechnology; CotB2; crystal structure; cyclooctatin; diterpene; reaction mechanism; terpene synthase; Introduction Terpenes represent one of the most diverse groups of natural biomolecules
- , antibiotic, neuroprotective and even insecticidal activities, which makes these compounds high-value commercial targets for the chemical and pharmaceutical industry [9][10]. Structural diversity of diterpenes is created by the terpene synthase (TPS) enzyme family, which use acyclic isoprenoid precursors to
- ) [12] to the acyclic terpene synthase substrate geranylgeranyl diphosphate 3 (GGDP) [1][13][14][15][16]. Following initial substrate binding and folding in a product-like conformation, the cyclization reaction can be subdivided into three steps: (1) generation of a reactive allyl carbocation as a
Harnessing enzyme plasticity for the synthesis of oxygenated sesquiterpenoids
Beilstein J. Org. Chem. 2019, 15, 2184–2190, doi:10.3762/bjoc.15.215
- -FDPs to sesquiterpenoids that may have applications in healthcare and agriculture. These results inform us of both the utility and limitations that non-natural functional groups have upon terpene cyclase-catalysed reaction cascades supporting the design of future biocatalytic syntheses. In particular
- biosynthetic reaction order is expandable to other terpene synthases to generate libraries of unnatural sesquiterpenoids with a wide range of potential uses and applications across many areas of human activity. Total-ion chromatogram of the pentane extractable products formed in an incubation of ADS with 8
Genome mining in Trichoderma viride J1-030: discovery and identification of novel sesquiterpene synthase and its products
Beilstein J. Org. Chem. 2019, 15, 2052–2058, doi:10.3762/bjoc.15.202
- invertebrates [1][2]. More than 80,000 terpenoids have been identified and characterised [3][4][5]. These diverse and complex natural products are mostly derived from carbocation cyclisation with linear C5 isoprene precursors, which are catalysed by terpene synthases (TPSs) [6]. TPSs can be classified into
- . Four (10%) and eight (7%) membered ring structures (e.g. asteriscanolide) are seldom found [14]. With the lower costs of gene sequencing, recent developments in genome mining by sequencing and annotation have led to the discovery of a large number of functionally unknown terpene synthases [15][16][17
- products, heterologous expression of various sources of terpene synthases in Escherichia coli and Saccharomyces cerevisiae is a feasible approach [25][26]. In this study, a combination of genome mining and metabolic engineering was used for sesquiterpenoid discovery, utilizing farnesyl diphosphate
Bipolenins K–N: New sesquiterpenoids from the fungal plant pathogen Bipolaris sorokiniana
Beilstein J. Org. Chem. 2019, 15, 2020–2028, doi:10.3762/bjoc.15.198
- Cochliobolus sp.) [1][26], were reported in B. sorokiniana for the first time, while, known metabolites 6 and 7 [20], 9 [34], 11 [2], and 12 [16] were previously reported from B. sorokiniana (syn. C. sativus and H. sativum). The terpene synthase responsible for the biosynthesis of the sativene/longifolene
- backbone of 1–11 remains unknown. Given that the genome of B. sorokiniana BRIP10943 has been sequenced [14], we surveyed the genome for potential terpene synthases that may be responsible for the biosynthesis of these compounds. Four putative sesquiterpene synthases were found, corresponding to the genes
- biosynthetic gene cluster (tpc) for terpestacin (12) has been recently identified from Bipolaris maydis [36]. A didomain sesterterpene synthase (tpcA) with a terpene cyclase domain and polyprenyltransferase domain was demonstrated to be responsible for the production of the sesterterpene backbone of 12. A
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)
Beilstein J. Org. Chem. 2019, 15, 1945–1961, doi:10.3762/bjoc.15.190
- NPP are possible as intermediates of terpene biosynthesis, since the absolute configurations of their products from Vitis vinifera L. are unknown and the subsequent cyclisation reactions can be explained by the enantiomers of germacrene D [30][31]. In order to investigate whether the formation of δ
Archangelolide: A sesquiterpene lactone with immunobiological potential from Laserpitium archangelica
Beilstein J. Org. Chem. 2019, 15, 1933–1944, doi:10.3762/bjoc.15.189
- period of 72 h during which the crystals were formed. These were collected by filtration over a frit and washed with hexanes obtaining 7.9 g of the matter that was analyzed by TLC and LRMS analyses. We observed that the matter consisted, in particular, of two terpene-type compounds, compound 1 and 2, and
- ; TNF-α, tumor necrosis factor alpha; SCE, supercritical CO2 extraction; SL, sesquiterpene lactones. Comment on nomenclature This article uses semitrivial terpene nomenclature and hence the numbering of compounds atoms may differ from these obtained by using IUPAC names. The structure of the
Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade
Beilstein J. Org. Chem. 2019, 15, 1890–1897, doi:10.3762/bjoc.15.184
- 351-0198, Japan Graduate School of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan 10.3762/bjoc.15.184 Abstract We previously showed that the regio- and stereoselectivity in terpene-forming reactions are determined by the conformations of the carbocation
- these two methyl groups are critical for the preorganization of GFPP in the biosynthetic pathways leading to sesterfisherol and quiannulatene. Keywords: biosynthesis; carbocation; DFT; substrate recognition; terpene cyclase; Introduction Terpene synthases are thought to have four main roles: (i
- terpene cyclase active site [3][5][6]. Although many terpene cyclases are known [6][7][8][9][10], it is still challenging to identify the precise initial conformation of the oligoprenyl diphosphate substrate in the active site, even by X-ray crystal structure determination. This is because the substrate
Phylogenomic analyses and distribution of terpene synthases among Streptomyces
Beilstein J. Org. Chem. 2019, 15, 1181–1193, doi:10.3762/bjoc.15.115
- /bjoc.15.115 Abstract Terpene synthases are widely distributed among microorganisms and have been mainly studied in members of the genus Streptomyces. However, little is known about the distribution and evolution of the genes for terpene synthases. Here, we performed whole-genome based phylogenetic
- analysis of Streptomyces species, and compared the distribution of terpene synthase genes among them. Overall, our study revealed that ten major types of terpene synthases are present within the genus Streptomyces, namely those for geosmin, 2-methylisoborneol, epi-isozizaene, 7-epi-α-eudesmol, epi-cubenol
- , caryolan-1-ol, cyclooctat-9-en-7-ol, isoafricanol, pentalenene and α-amorphene. The Streptomyces species divide in three phylogenetic groups based on their whole genomes for which the distribution of the ten terpene synthases was analysed. Geosmin synthases were the most widely distributed and were found
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