Confirmation of the stereochemistry of spiroviolene

• Yao Kong,
• Yuanning Liu,
• Kaibiao Wang,
• Tao Wang,
• Chen Wang,
• Ben Ai,
• Hongli Jia,
• Guohui Pan,
• Min Yin and
• Zhengren Xu

Beilstein J. Org. Chem. 2024, 20, 852–858, doi:10.3762/bjoc.20.77

• stereochemistry by X-ray crystallography using a hydrazone derivative of 1. Results and Discussion Our work commenced with the heterologous production of spiroviolene by E. coli using a recently developed isopentenol utilization pathway for the efficient supply of two C5 precursors for terpene biosynthesis

Unraveling the role of prenyl side-chain interactions in stabilizing the secondary carbocation in the biosynthesis of variexenol B

• Moe Nakano,
• Rintaro Gemma and
• Hajime Sato

Beilstein J. Org. Chem. 2023, 19, 1503–1510, doi:10.3762/bjoc.19.107

Navigating and expanding the roadmap of natural product genome mining tools

• Friederike Biermann,
• Sebastian L. Wenski and
• Eric J. N. Helfrich

Beilstein J. Org. Chem. 2022, 18, 1656–1671, doi:10.3762/bjoc.18.178

• ])) [28]. In contrast, discrete multi-enzymatic assemblies utilize distinct, monofunctional enzymes. Examples are terpene (e.g., cyclooctatin (8) [29]), ribosomally synthesized and post-translationally modified peptide (RiPP), or NRPS-independent alkaloid pathways. In the case of terpene biosynthesis

The enzyme mechanism of patchoulol synthase

• Houchao Xu,
• Bernd Goldfuss,
• Gregor Schnakenburg and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2022, 18, 13–24, doi:10.3762/bjoc.18.2

• 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

3-Acetoxy-fatty acid isoprenyl esters from androconia of the ithomiine butterfly Ithomia salapia

• Florian Mann,
• Daiane Szczerbowski,
• Lisa de Silva,
• Melanie McClure,
• Marianne Elias and
• Stefan Schulz

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

Bacterial terpene biosynthesis: challenges and opportunities for pathway engineering

• Eric J. N. Helfrich,
• Geng-Min Lin,
• Christopher A. Voigt and
• Jon Clardy

Beilstein J. Org. Chem. 2019, 15, 2889–2906, doi:10.3762/bjoc.15.283

• 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

• . Keywords: bacterial sesquiterpenes and diterpenes; cytochrome P450; pathway engineering; synthetic biology; terpene biosynthesis; terpene cyclase; Introduction Evolutionary diversification of terpene biosynthetic pathways has resulted in the largest and most structurally diverse class of specialized

• can be further modified by tailoring enzymes, but the core structure can be inferred from the organization of the biosynthetic genes and the modular architecture of the associated proteins [7][8]. Terpene biosynthesis has a very different logic. Five-carbon units called isoprenes are joined to create

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

• 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

• extraction temperatures. In our study, we aimed I) to determine whether P. polycephalum releases volatile terpenoids under normal growing conditions and II) to identify and characterize the genes for terpene biosynthesis in P. polycephalum. Our results will enable us to compare terpene chemistry and their

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

• in terpene biosynthesis. The enzyme could be understood as passive catalyst, essentially chaperoning the intermediates during the reaction cascade. It is clear that much of terpene biosynthesis can be understood by this concept. “Inherent reactivity” largely relies on theoretical calculations

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)

• Philipp P. Könen and
• Matthias Wüst

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

Correction: Dynamic behavior of rearranging carbocations – implications for terpene biosynthesis

• Stephanie R. Hare and
• Dean J. Tantillo

Beilstein J. Org. Chem. 2017, 13, 1669–1669, doi:10.3762/bjoc.13.161

Opportunities and challenges for the sustainable production of structurally complex diterpenoids in recombinant microbial systems

• Katarina Kemper,
• Max Hirte,
• Markus Reinbold,
• Monika Fuchs and
• Thomas Brück

Beilstein J. Org. Chem. 2017, 13, 845–854, doi:10.3762/bjoc.13.85

• with recombinant terpene biosynthesis modules, they are very suitable hosts for heterologous production of high value terpenes. Yet, in contrast to the number of extracted and characterized terpenes, little is known about the specific biosynthetic enzymes that are involved especially in the formation

• successful establishment of heterologous terpene production in a bacterial host is given in Figure 1. Conclusion Over the last years, countless and in some cases ground-breaking studies about terpenes and heterologous terpene biosynthesis have been published, and it still seems like just the tip of the

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

• terpene biosynthesis gene clusters. The genus Haliangium Haliangium ochraceum sp. nov. (initially termed H. luteum, DSM 14365T) and H. tepidum sp. nov. (DSM 14436T) were isolated from seaweed and sea grass, respectively, with both samples being obtained from a sandy beach in Miura, Japan by Fudou et al

Dynamic behavior of rearranging carbocations – implications for terpene biosynthesis

• Stephanie R. Hare and
• Dean J. Tantillo

Beilstein J. Org. Chem. 2016, 12, 377–390, doi:10.3762/bjoc.12.41

• theoretical tools. Then we describe studies dealing with carbocations that are not involved in terpene formation, but which reveal reactivity principles that may have implications for terpene biosynthesis. This is followed by descriptions of the relatively few studies published so far that are concerned with

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

• prominent example of the deoxyxylulose phosphate way in terpene biosynthesis [7][8]. Thus, a critical analysis of labeling experiments is required and may hint towards undiscovered metabolic pathways or enzyme functions [9]. As demonstrated in this article, the isotopic labeling technique continues to be an

• skeletons (Figure 6). The fascination of terpene biosynthesis arises from the complexity and variety of carbon scaffolds, terpene cyclases are able to build up using few linear oligoprenyl diphosphate precursors. This promotes investigations using isotopically labeled compounds both on acetate- and

• diterpenoid product cyclooctat-9-en-7-ol (52). Further oxidation by the cytochrome P450-hydroxylases CotB3 and CotB4 yields the biologically active compound cyclooctatin (45) [67]. This outstanding study exemplifies the scope of isotopic labeling experiments in the elucidation of terpene biosynthesis by

[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

• terpene biosynthesis using stable isotope labellings prompted us to investigate whether it is possible to obtain a fully deuterated terpene by culturing a bacterium in a 100% deuterated medium. Here we report the successful production of the first completely deuterated terpene by fermentation and discuss

Tertiary alcohol preferred: Hydroxylation of trans-3-methyl-L-proline with proline hydroxylases

• Christian Klein and
• Wolfgang Hüttel

Beilstein J. Org. Chem. 2011, 7, 1643–1647, doi:10.3762/bjoc.7.193

• ]. Other less common approaches include stereospecific enzyme-catalyzed hydrolyses of epoxides, stereoselective additions to ketones with hydroxynitrile lyases or carboligases, and the application of enzymes involved in terpene biosynthesis, such as dehydratases, cyclases or transferases [6][8]. An