Germacrene B – a central intermediate in sesquiterpene biosynthesis

• Houchao Xu and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2023, 19, 186–203, doi:10.3762/bjoc.19.18

• (+)-α-vetivone (43) (Scheme 12C) [96][97] and isovalencenic acid (45) (Scheme 12D) [98] were correlated to this hydrocarbon. Recently, an iron catalyst has been developed that was applied in the isomerisation of valencene (48) to 39 (Scheme 12E) [99]. The biogenesis of 40 would be possible from I2a

Targeting the Pseudomonas quinolone signal quorum sensing system for the discovery of novel anti-infective pathoblockers

• Christian Schütz and
• Martin Empting

Beilstein J. Org. Chem. 2018, 14, 2627–2645, doi:10.3762/bjoc.14.241

• molecule [34]. This autoinducer has been described to mediate iron acquisition, cytotoxicity, outer-membrane vesicle biogenesis, and to exert host immune modulatory effects [34][35]. Interestingly, PQS as well as HHQ are able to interfere with nuclear transcription factor-κB and hypoxia-inducible factor 1

An overview of recent advances in duplex DNA recognition by small molecules

• Sayantan Bhaduri,
• Nihar Ranjan and
• Dev P. Arya

Beilstein J. Org. Chem. 2018, 14, 1051–1086, doi:10.3762/bjoc.14.93

• carrier of genetic information, the DNA double helix interacts with many natural ligands during the cell cycle, and is amenable to such intervention in diseases such as cancer biogenesis. Proteins bind DNA in a site-specific manner, not only distinguishing between the geometry of the major and minor

Are boat transition states likely to occur in Cope rearrangements? A DFT study of the biogenesis of germacranes

• José Enrique Barquera-Lozada and
• Gabriel Cuevas

Beilstein J. Org. Chem. 2017, 13, 1969–1976, doi:10.3762/bjoc.13.192

• stable elemanolide that is even more stable than its (Z,E)-germacrane. Keywords: biogenesis; density functional theory; reaction mechanism; sigmatropic rearrangement; terpenes; Introduction Germacranes are biogenetic precursors of elemanes [1][2][3][4], because germacranes can be easily transformed

• energetic evolution of germacranolides’ Cope transformations. Computational methods DFT has been proved to be a good method for the study of reaction mechanisms of natural products' biogenesis and it has been used in many studies [44][45][46][47][48][49][50][51][52][53][54][55] and it is the method of

• choice for pericyclic reactions studies [20][56]. In particular, third generation hybrid functionals have improved the description of the potential energy surface and produce very reliable results [57][58][59][60]. Our studies in terpene biogenesis show that these hybrid functionals competes successfully

Framing major prebiotic transitions as stages of protocell development: three challenges for origins-of-life research

• Ben Shirt-Ediss,
• Sara Murillo-Sánchez and
• Kepa Ruiz-Mirazo

Beilstein J. Org. Chem. 2017, 13, 1388–1395, doi:10.3762/bjoc.13.135

• Conceiving the process of biogenesis as the evolutionary development of highly dynamic and integrated protocell populations provides the most appropriate framework to address the difficult problem of how prebiotic chemistry bridged the gap to full-fledged living organisms on the early Earth. In this

• these two fundamental aspects of biological phenomenology (the organisational and evolutionary aspects) can be brought together by means of a general scheme of prebiotic transitions that puts ‘protocells’ at the very centre, as the prime axis of the process of biogenesis (see Figure 1). Furthermore, we

• across all living domains [7], could be present at the first stages of biogenesis. Such complex membrane mechanisms were, no doubt, latecomers – highly optimized products of evolution. However, any plausible evolutionary explanation of their emergence should begin with simpler lipid compartments and with

Characterization of non-heme iron aliphatic halogenase WelO5* from Hapalosiphon welwitschii IC-52-3: Identification of a minimal protein sequence motif that confers enzymatic chlorination specificity in the biosynthesis of welwitindolelinones

• Qin Zhu and
• Xinyu Liu

Beilstein J. Org. Chem. 2017, 13, 1168–1173, doi:10.3762/bjoc.13.115

• engineering and evolution of these proteins for biocatalyst application. Keywords: alkaloid biogenesis; biosynthetic divergency; C–H activation; halogenase; non-heme iron enzyme; Introduction Carbon–halogen (C–X) bonds are prevalent structural motifs in modern agrochemicals, pharmaceuticals and bioactive

• ], analogous oxidative functionalizations with halogens via C–H activations remain challenging that need to be addressed [9][10][11]. Recently, during the systematic investigation of hapalindole-type alkaloid biogenesis [12][13][14][15][16][17][18][19], we discovered a family of Fe/2OG-dependent halogenases

• that can oxidatively monochlorinate aliphatic carbon centers in freestanding molecules, typified by WelO5 protein in the biogenesis of welwitindolinones [17]. This discovery provided a new opportunity to utilize protein catalysts for late-stage halogenations of unactivated carbons in bioactive small

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

• diverse biological activities [72] together with its broadly unexplored biogenesis [73][74] motivated many synthetic groups to develop total syntheses of cis-solamin A (29) [75][76][77][78][79][80][81][82][83] and B [76][78][83]. In 2002, Brown and co-workers achieved concise total syntheses of cis

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

• section, we present a biosynthetic proposal, discuss various synthetic approaches towards xenicane diterpenoids and highlight successful total syntheses. Review Biosynthetic hypothesis The proposed biogenesis of xenicanes (Scheme 1) is suggested to be similar to the reported biosynthesis of the

Biocatalysis for the application of CO₂ as a chemical feedstock

• Apostolos Alissandratos and
• Christopher J. Easton

Beilstein J. Org. Chem. 2015, 11, 2370–2387, doi:10.3762/bjoc.11.259

• to prepare tobacco plants that expressed cyanobacterial RuBisCO together with a protein that forms part of the carboxysomal structure, which led to the generation of macromolecular complexes that are observed early in the carboxysomal biogenesis in cyanobacteria. In addition, the engineered plants

Total synthesis of panicein A₂

• Lili Yeung,
• Lisa I. Pilkington,
• Melissa M. Cadelis,
• Brent R. Copp and
• David Barker

Beilstein J. Org. Chem. 2015, 11, 1991–1996, doi:10.3762/bjoc.11.215

• with the earlier report that stated 5 exhibits in vitro cytotoxicity against a number of cell lines (ED50 = 5 μg/mL). Members of the panicein family of aromatic sesquiterpenoids. Proposed biogenesis of panicein A2 (5). Retrosynthetic analysis of panicein A2 (5). Synthesis of ketone 13. Synthesis of

New sesquiterpene hydroquinones from the Caribbean sponge Aka coralliphagum

• Qun Göthel and
• Matthias Köck

Beilstein J. Org. Chem. 2014, 10, 613–621, doi:10.3762/bjoc.10.52

• siphonodictyal E4 (4a). Proposed biogenesis of 4a starting from the hypothetical precursor 3-ox with an acyclic sesquiterpenoid part. Hypothetical biogenesis of the bicyclic sesquiterpenoid moiety from the acyclic precursor of the siphonodictyals in the sponge Aka coralliphagum [11]. The newly formed bonds from

The chemistry of isoindole natural products

• Klaus Speck and
• Thomas Magauer

Beilstein J. Org. Chem. 2013, 9, 2048–2078, doi:10.3762/bjoc.9.243

• representatives of this distinct class of natural products, has been studied extensively and reviewed by Knölker and Ōmura [17][22]. The biogenesis of staurosporine (26) is outlined in Scheme 3. Biosynthetically, the indolocarbazole scaffold is derived from two fused tryptophan molecules, whereas the sugar moiety

• is derived from L-tryptophan (36) [25], indicate a close biosynthetic relationship between these alkaloids. After additional experiments, the authors concluded that lycogalic acid A (38) is the biosynthetic key intermediate for the biogenesis of indolocarbazoles. This hypothesis was verified through

• ], the isoquinoline nuevamine (96) [77] and the benzazocine magallanesine (97) [79] were isolated from different Berberidaceae species (Figure 6). Chilenine (93) was the first isoindolobenzazepine alkaloid isolated from Berberis empetrifolia in 1982. The biogenesis proceeds most likely via a Pictet

Study on the total synthesis of velbanamine: Chemoselective dioxygenation of alkenes with PIFA via a stop-and-flow strategy

• Huili Liu,
• Kuan Zheng,
• Xiang Lu,
• Xiaoxia Wang and
• Ran Hong

Beilstein J. Org. Chem. 2013, 9, 983–990, doi:10.3762/bjoc.9.113

• leukemia [12][13][14]. Fragmentation of 3 under acidic conditions delivers two structural units, desacetylvindoline and velbanamine (2) [15]. The reassembling of catharanthine (1) and vindoline (5) into the parent alkaloids 3 and 4 by using FeCl3-promoted oxidative coupling supports the biogenesis of

Biosynthesis and function of secondary metabolites

• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2011, 7, 1620–1621, doi:10.3762/bjoc.7.190

• biogenesis. Biosynthetic aspects are closely related to functional investigations, because a deep understanding of metabolic pathways to natural products, not only on a chemical, but also on a genetic and enzymatic level, allows for the expression of whole biosynthetic gene clusters in heterologous hosts

A short synthesis of (±)-cherylline dimethyl ether

• Bhima Y. Kale,
• Ananta D. Shinde,
• Swapnil S. Sonar,
• Bapurao B. Shingate,
• Sanjeev Kumar,
• Samir Ghosh,
• Soodamani Venugopal and
• Murlidhar S. Shingare

Beilstein J. Org. Chem. 2009, 5, No. 80, doi:10.3762/bjoc.5.80

• long been fascinating targets for organic chemists as witnessed by a number of articles dealing with biogenesis, isolation, characterization and synthesis. Cherylline (1) and latifine (2) are the two 4-aryltetrahydroisoquinoline alkaloids isolated from Amaryllidaceae plants. Apart from their natural