Emission and biosynthesis of volatile terpenoids from the plasmodial slime mold Physarum polycephalum

• Xinlu Chen,
• Tobias G. Köllner,
• Wangdan Xiong,
• Guo Wei and
• Feng Chen

Beilstein J. Org. Chem. 2019, 15, 2872–2880, doi:10.3762/bjoc.15.281

• investigated Physarum polycephalum, a plasmodial slime mold also known as acellular amoeba. Plasmodia of P. polycephalum grown on agar plates were found to release a mixture of volatile terpenoids consisting of four major sesquiterpenes (α-muurolene, (E)-β-caryophyllene, two unidentified sesquiterpenoids) and

• 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

• diverse VOCs, terpenoids are the largest group. Terpenoids are biosynthesized from two C5 diphosphate compounds isopentenyl diphosphate (IPP) and its isomer dimethylallyl diphosphate (DMAPP), which are produced by either the mevalonate (MVA) pathway or the methylerythritol phosphate (MEP) pathway [9][10

Nanangenines: drimane sesquiterpenoids as the dominant metabolite cohort of a novel Australian fungus, Aspergillus nanangensis

• Heather J. Lacey,
• Cameron L. M. Gilchrist,
• Andrew Crombie,
• John A. Kalaitzis,
• Daniel Vuong,
• Peter J. Rutledge,
• Peter Turner,
• John I. Pitt,
• Ernest Lacey,
• Yit-Heng Chooi and
• Andrew M. Piggott

Beilstein J. Org. Chem. 2019, 15, 2631–2643, doi:10.3762/bjoc.15.256

• : Aspergillus; biosynthesis; drimane; secondary metabolites; sesquiterpenoid; terpenes; Introduction The fungal genus Aspergillus is well recognised as a source of structurally diverse terpenoids comprising monoterpenoids [1], sesquiterpenoids [2][3][4][5], diterpenoids [6], sesterterpenoids [7][8][9

• production of terpenoids as the dominant biosynthetic class of secondary metabolites. Results and Discussion Purification and identification The metabolite profile of A. nanangensis was examined on a limited range of solid and liquid media suitable for fungal metabolite production. The metabolite profile

• column bed (55 × 250 mm). The column was eluted with CHCl3 (500 mL) containing increasing concentrations of MeOH. The fractions containing terpenoids (0-2% MeOH, 3.0 g) were pooled and fractionated using isocratic preparative HPLC (Zorbax C18, 65% MeCN/H2O, 60 mL min–1) to give five fractions containing

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

• and terpenoids. For thousands of years mankind mainly used plant extracts to collect ingredients for the creation of perfumes. Many of these extracts contain complex mixtures of terpenes, that show distinct olfactoric properties as pure compounds. When organic synthesis appeared on the scene, the

• : asymmetric synthesis; fragrances; odorants; sandalwood; scents; terpenes; terpenoids; Review “Iso E Super® is to perfume what Tango Nuevo is to Tango Argentino” [1] Introduction – classical terpenes in perfumes Perfumes (Latin “per fumus”, which means “through smoke”) have accompanied mankind for thousands

• ]. Following this invention, many derivatives were produced to find new viable targets. These studies mostly focused on Diels–Alder cycloadditions to create structures that resemble terpenoids readily available from easily accessible and affordable starting materials like myrcene (1). One of the newly found

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

• ]. Yet another approach is the use of heteroatom-modified farnesyl diphosphates that could be still cyclized by TPSs yielding unnatural terpenoids [105]. CotB1 synthesizes geranylgeranyl diphosphate (GGDP) 3 from the substrates dimethylallyl diphosphate (DMAPP) 1 and isopentenyl diphosphate (IPP) 2. The

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

• hydrocarbons, substituted cyclic molecules, terpenoids, and steroid derivatives, were selectively fluorinated at some otherwise inaccessible sites, however, in low to moderate yields. On the other hand, the same group [83] developed Mn(salen)Cl as a catalyst for the direct C–H fluorination at benzylic

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

• of them being the marine-adapted fungal strain Heydenia cf. alpina. The latter produced two new terpenoids, which are the first secondary metabolites from this genus. Keywords: FIND; fungal one-step isolation device; Heydenia cf. alpina; natural products; terpenes; Introduction Natural products

Harnessing enzyme plasticity for the synthesis of oxygenated sesquiterpenoids

• Melodi Demiray,
• David J. Miller and
• Rudolf K. Allemann

Beilstein J. Org. Chem. 2019, 15, 2184–2190, doi:10.3762/bjoc.15.215

• synthesised in amorphadiene synthase-catalysed reactions from 8- and 12-methoxyfarnesyl diphosphates due to the highly plastic yet tightly controlled carbocationic chemistry of this sesquiterpene cyclase. Keywords: artemisinin; amorphadiene synthase; oxygenated terpenoids; sesquiterpenoids; substrate

• and functional groups to generate unnatural sesquiterpenoids that are not easily accessible by conventional organic synthesis [10][11][12][13][14][15][16][17][18][19]. Creating novel sesquiterpenoids, not normally found in nature, is of great interest due to the important applications of terpenoids in

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

• synthases in Trichoderma viride have been seldom studied, despite the efficiency of filamentous fungi for terpenoid production. Using the farnesyl diphosphate-overexpressing Saccharomyces cerevisiae platform to produce diverse terpenoids, we herein identified an unknown sesquiterpene synthase from T. viride

• . viride to date. Keywords: genome mining; metabolic engineering; natural products; sesquiterpene synthase; terpenes; Trichoderma viride J1-030; Introduction Terpenoids represent the most diverse group of natural products, with a wide distribution in microorganisms, plants, insects and various marine

• 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

Phylogenomic analyses and distribution of terpene synthases among Streptomyces

• Lara Martín-Sánchez,
• Kumar Saurabh Singh,
• Mariana Avalos,
• Gilles P. van Wezel,
• Jeroen S. Dickschat and
• Paolina Garbeva

Beilstein J. Org. Chem. 2019, 15, 1181–1193, doi:10.3762/bjoc.15.115

• remarkable genetic potential to produce a large variety of secondary metabolites with different functions including antibiotics, antifungals, pigments or immunosuppressants [1][2][3]. These are compounds of diverse chemical nature such as polyketides, peptides, aminoglycosides or terpenoids [4][5

• ]. Terpenoids are the largest and the most diverse class of natural compounds known to date and include the initial products of terpene synthases and all derivatives made from them in tailoring steps. This very diverse class of organic compounds is best known as plant metabolites. However, recent studies

• revealed that terpenoids can be produced by all kingdoms of life including bacteria, fungi and protists [6][7][8][9][10]. The ability of an organism to produce terpenoids relies on whether the organism contains terpene synthase genes. Biosynthetically, the production of the different types of terpenes

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

• secondary metabolite profiles of C. aegerita, we found several terpenoids in submerged cultures. Aside from the main metabolite, bovistol (1), two new bovistol derivatives B and C (2, 3) and pasteurestin C as a new protoilludane (4) were isolated by preparative HPLC. Their structures were elucidated by mass

• strains, targeting both volatile and non-volatile compounds. The present paper will describe the discovery of one known and three new non-volatile terpenoids (Figure 1) that were isolated from liquid cultures of C. aegerita and their physicochemical and preliminary biological characterisation. Results and

Iodine(III)-mediated halogenations of acyclic monoterpenoids

• Laure Peilleron,
• Tatyana D. Grayfer,
• Joëlle Dubois,
• Robert H. Dodd and
• Kevin Cariou

Beilstein J. Org. Chem. 2018, 14, 1103–1111, doi:10.3762/bjoc.14.96

• potential of the latter two vicinal difunctionalizations of terpenoids by not only expanding their substrate scope but also by trying to achieve other bromo-oxylations as well as analogous chloro- and/or iodofunctionalizations of linear terpenoids. For this purpose, five monoterpene derivatives – bearing

• Discussion Optimizations In order to carry out the exploration of the various halogenations that could be performed, geranyl acetate (1a) was chosen as the model substrate. In our study on terpenoids [16], the reaction conditions for the dibromination of the distal double bond were easily established from

• formation of allylic chloride 6. Conclusion Overall, we have further extended the scope of the iodine(III)-mediated oxidative halogenation of terpenoids which now includes dibromination, bromo(trifluoro)acetoxylation, bromohydroxylation, iodo(trifluoro)acetoxylation and allylic ene-chlorination. The

Herpetopanone, a diterpene from Herpetosiphon aurantiacus discovered by isotope labeling

• Xinli Pan,
• Nicole Domin,
• Sebastian Schieferdecker,
• Hirokazu Kage,
• Martin Roth and
• Markus Nett

Beilstein J. Org. Chem. 2017, 13, 2458–2465, doi:10.3762/bjoc.13.242

• resemblance to cadinane-type sesquiterpenes from plants, but is structurally entirely unprecedented in bacteria. Based on its molecular architecture, a possible biosynthetic pathway is postulated. Keywords: genome mining; herpetopanone; Herpetosiphon; isotope labeling; terpene; Introduction Terpenoids

• represent the largest group of natural products with about 60,000 different compounds being known. They occur in all three domains of life and are known to fulfill a variety of different functions, e.g., as membrane constituents, chemical attractants or feeding deterrents [1]. Over a long period, terpenoids

• were mainly reported from plants and, to a lesser degree, also from fungi and marine invertebrates. In recent years, however, the discovery of terpenoids from prokaryotes has gained momentum. The ease of DNA sequencing has strongly favored this development, contributing to the identification of

Biosynthetic origin of butyrolactol A, an antifungal polyketide produced by a marine-derived Streptomyces

• Enjuro Harunari,
• Hisayuki Komaki and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2017, 13, 441–450, doi:10.3762/bjoc.13.47

• diverse secondary metabolites with pharmaceutically useful bioactivities. Importantly, members of the genus Streptomyces have been the main source of drug discovery programs due to their high capacity in secondary metabolism including polyketides, peptides, terpenoids, alkaloids, and amino acid

A detailed view on 1,8-cineol biosynthesis by Streptomyces clavuligerus

• Jan Rinkel,
• Patrick Rabe,
• Laura zur Horst and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2016, 12, 2317–2324, doi:10.3762/bjoc.12.225

• complexity is reached within the largest, the terpenoids. An estimated number of 75,000 different compounds are known from all kinds of organisms including plants [1], bacteria [2][3][4][5], fungi [6] and, as recently shown, even social amoebae [7]. These molecules are all made from only a handful of linear

• representing various stereoisomers and constitutional isomers with different positioning of olefinic double bonds or alcohol functions are known just for sesquiterpenes [11]. The structural diversity of terpenoids can be further increased by the action of tailoring enzymes such as cytochrome P450

The direct oxidative diene cyclization and related reactions in natural product synthesis

• Juliane Adrian,
• Leona J. Gross and
• Christian B. W. Stark

Beilstein J. Org. Chem. 2016, 12, 2104–2123, doi:10.3762/bjoc.12.200

• , polyketides, amino acids, fatty acids as well as acetogenins and terpenoids) are summarized in this review article. Putative structures of geraniol 1a (R = H) or 1b (R = H) (in 1924), their expected dihydroxylation products 2a or 2b and the true structure 3 as determined by Klein and Rojahn in 1965 [8

Mechanistic investigations on six bacterial terpene cyclases

• Patrick Rabe,
• Thomas Schmitz and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2016, 12, 1839–1850, doi:10.3762/bjoc.12.173

• much later, with the first described compounds being geosmin [3] and 2-methylisoborneol [4], two irregular terpenoids that represent a degraded sesquiterpene [5] and a methylated monoterpene [6], respectively. These compounds have a musty or earthy aroma and are responsible for the smell of freshly

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

• [4]. Oxygen heterocycles are mainly found in carbohydrates, polyketides, peptides and terpenoids. Nitrogen heterocycles are part of peptides and alkaloids. Both can of course also occur in the respective hybrid natural products. Sulphur-containing heterocycles are present in few polyketides and more

• [138][139]. With the exception of a few terpenoids, most tetronates are of polyketide origin, either being completely biosynthesised by a PKS or by hijacking intermediates from fatty acid biosynthesis (Figure 6). Although the larger body of tetronates is produced by Actinobacteria, they are abundant in

Marine-derived myxobacteria of the suborder Nannocystineae: An underexplored source of structurally intriguing and biologically active metabolites

• Antonio Dávila-Céspedes,
• Peter Hufendiek,
• Max Crüsemann,
• Till F. Schäberle and
• Gabriele M. König

Beilstein J. Org. Chem. 2016, 12, 969–984, doi:10.3762/bjoc.12.96

• solvents upon light exposure [62]. The salimyxins represent the third group of compounds, i.e., salimyxin A (29) and B (30). These belong to a subgroup of terpenoids named incisterols, which were first discovered from the sponge Dictyonella incisa [63]. Their biosynthesis presumably involves oxidative

Three new trixane glycosides obtained from the leaves of Jungia sellowii Less. using centrifugal partition chromatography

• Luíse Azevedo,
• Larissa Faqueti,
• Marina Kritsanida,
• Antonia Efstathiou,
• Despina Smirlis,
• Gilberto C. Franchi Jr,
• Grégory Genta-Jouve,
• Sylvie Michel,
• Louis P. Sandjo,
• Raphaël Grougnet and
• Maique W. Biavatti

Beilstein J. Org. Chem. 2016, 12, 674–683, doi:10.3762/bjoc.12.68

• the polyphenols identified in Jungia species, sesquiterpenoids with guaiane, guaiene, nortrixane, trixane (isocedrene), and cyperane scaffolds are also representative of this genus [6][7][8][9]. These terpenoids demonstrated a wide range of bioactivities [10][11][12], and hit compounds such as

Synthesis of Xenia diterpenoids and related metabolites isolated from marine organisms

• Tatjana Huber,
• Lara Weisheit and
• Thomas Magauer

Beilstein J. Org. Chem. 2015, 11, 2521–2539, doi:10.3762/bjoc.11.273

• nine-membered carbocycle which is the characteristic structural feature of these natural products. Additionally, the putative biosynthetic pathway of xenicanes is illustrated. Keywords: asymmetric synthesis; natural products; total synthesis; Xenia diterpenoids; xenicanes; Introduction Terpenoids are

Recent highlights in biosynthesis research using stable isotopes

• Jan Rinkel and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2015, 11, 2493–2508, doi:10.3762/bjoc.11.271

• classes including polyketides, non-ribosomal peptides, their hybrids, terpenoids, and aromatic compounds formed via the shikimate pathway. The text does not aim at a comprehensive overview, but instead a selection of recent important examples of isotope usage within biosynthetic studies is presented, with

• these experiments in combination with genetic studies, the biosynthesis of thiomarinol A (27) proceeds via coupling of 4-hydroxybutyrate to the PKS product, two cycles of chain elongation and finally coupling with the NRPS product pyrrothine. Terpenes Terpenoids constitute the largest group of natural

• rearrangements and cyclizations experimentally. The structure elucidation of terpenoids can be challenging because of the multicyclic carbon skeletons with several contiguous stereocenters. The assistance of 13C labels can in such cases be especially helpful, and if completely 13C-labeled carbon backbones can be

Pyridinoacridine alkaloids of marine origin: NMR and MS spectral data, synthesis, biosynthesis and biological activity

• Louis P. Sandjo,
• Victor Kuete and
• Maique W. Biavatti

Beilstein J. Org. Chem. 2015, 11, 1667–1699, doi:10.3762/bjoc.11.183

• , terpenoids, phenolics, polysaccharides and alkaloids [4]. Various bioactivity functions such as anticancer [5][6][7], phytotoxicity [8][9][10][11], antioxidant [12][13][14][15][16], antimicrobial [17][18][19], analgesic [20][21], hypotensive [22], hypoglycemic [23], antiprotozoal [24] and plant protecting

An unusually stable chlorophosphite: What makes BIFOP–Cl so robust against hydrolysis?

• Roberto Blanco Trillo,
• Jörg M. Neudörfl and
• Bernd Goldfuss

Beilstein J. Org. Chem. 2015, 11, 313–322, doi:10.3762/bjoc.11.36

• , in Pd catalysts. Keywords: chirality; hydrolysis; phosphorus; rearrangements; terpenoids; Introduction Phosphorus halides are highly reactive intermediates for the synthesis of phosphites and phosphoramidites [1][2][3][4][5], which are widely used, for example, as ligands in catalysts [6][7][8][9

Stereoselective cathodic synthesis of 8-substituted (1R,3R,4S)-menthylamines

• Carolin Edinger,
• Jörn Kulisch and
• Siegfried R. Waldvogel

Beilstein J. Org. Chem. 2015, 11, 294–301, doi:10.3762/bjoc.11.34

• naturally occurring terpenoids is the reductive amination under Leuckart–Wallach conditions (see Scheme 2, pathway I) [39]. This method was applied to convert 2 to N-alkyl substituted menthylamines [40]. However, a significant disadvantage of this method is the lack of stereocontrol and partial inversion of

Synthesis of the furo[2,3-b]chromene ring system of hyperaspindols A and B

• Danielle L. Paterson and
• David Barker

Beilstein J. Org. Chem. 2015, 11, 265–270, doi:10.3762/bjoc.11.29

• been isolated from H. chinense including prenylated acylphloroglucinols such as chinesins I (3) and II (4), xanthones, flavonoids, terpenoids, naphthodianthrones, and norlignans, such as hyperione A (5) and B (6) [1][6][7][8]. Chinesins I (3) and II (4) are acylphloroglucinol derivatives which possess