Substrate specificity of a ketosynthase domain involved in bacillaene biosynthesis

• Zhiyong Yin and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2024, 20, 734–740, doi:10.3762/bjoc.20.67

• understanding of polyketide biosynthesis has been reached, including a detailed knowledge of the extender unit selection and the stereochemical implications that are predictable from amino acid sequences [5][6]. The polyene antibiotic bacillaene was first isolated from Bacillus subtilis [7]. This soil-dwelling

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

• biosynthesis → polyketide biosynthesis). As such, NP biosynthetic pathways utilize members of existing enzyme families that have evolved to perform new metabolic functions. Consequently, NP BGCs “borrow” genes encoding paralogs of enzymes that have their origin in primary metabolism and that have diverged into

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

• assist in refining our understanding of bacterial terpenoid biosynthesis. Examples of bioactive terpenoids. Repetitive electrophilic and nucleophilic functionalities in terpene and type II PKS-derived polyketide biosynthesis. a) Schematic representation. b) Type II PKS-derived polyketide biosynthesis. c

Isolation and biosynthesis of an unsaturated fatty acid with unusual methylation pattern from a coral-associated bacterium Microbulbifer sp.

• Amit Raj Sharma,
• Enjuro Harunari,
• Tao Zhou,
• Agus Trianto and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2019, 15, 2327–2332, doi:10.3762/bjoc.15.225

• fatty acid/polyketide biosynthesis. Compound 1 and its (2E,4E)-isomer were reported previously as synthetic compounds but this is the first finding of 1 as a natural product [12][21]. Very recently, benzoate derivatives were reported from a marine-derived Microbulbifer [22]. Therefore, this is the

Volatiles from the hypoxylaceous fungi Hypoxylon griseobrunneum and Hypoxylon macrocarpum

• Jan Rinkel,
• Alexander Babczyk,
• Tao Wang,
• Marc Stadler and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2018, 14, 2974–2990, doi:10.3762/bjoc.14.277

• derivatives. Their structures could only be unambiguously determined by comparison to all isomers with different substitution patterns. The substitution pattern of the main compound from H. griseobrunneum, the new natural product 2,4,5-trimethylanisole, was explainable by a polyketide biosynthesis mechanism

• (methyl-2H3)methionine. While the methylation pattern of the alternative structure 24c is difficult to understand via a polyketide biosynthesis mechanism, the formation of the assigned structure of 24 by a polyketide synthase (PKS) can be easily rationalised (Scheme 2). The acetate starter unit, bound to

• exhibited the mass spectra shown in Figure 4E and Figure 4F that were similar to database spectra of 2,5-dimethyl-p-anisaldehyde (25) and methyl 2,5-dimethyl-p-anisate (26). The substitution pattern of these compounds is well explained by polyketide biosynthesis logic (Scheme 3). Starting from ACP-bound

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

• -27). The origin of the tert-butyl group in polyketide biosynthesis is still unknown, however, the tert-butyl functionality of bottromycin and polytheonamide was shown to be produced by radical C-methylation of the isopropyl group of valine [31][32]. By analogy, the tert-butyl portion of 1 was most

Polyketide stereocontrol: a study in chemical biology

• Kira J. Weissman

Beilstein J. Org. Chem. 2017, 13, 348–371, doi:10.3762/bjoc.13.39

• the final polyketide products could arise by judicious choice by the PKS AT domains of one or the other enantiomer. The first information on extender unit selection in polyketide biosynthesis was provided in the mid-1980s via feeding of isotopically-labeled precursors to whole cells of the

• -methylacetoacetate) showed this reaction to be rapid at room temperature (t1/2 = 4.7 min) [82]. Thus, during polyketide biosynthesis, there must be some mechanism to protect the intermediate from spontaneous epimerization following chain extension, both as it is passed between the KS and KR active sites and within

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

• ). This review intends to give an overview on the mechanisms involved in heterocycle formation during polyketide biosynthesis. A focus will be placed on oxygen and nitrogen-containing heterocycles due to their abundance and relevance. Although the genuine polyketide biosynthesis machinery does not harbour

Biosynthesis of α-pyrones

• Till F. Schäberle

Beilstein J. Org. Chem. 2016, 12, 571–588, doi:10.3762/bjoc.12.56

• ellagitannin biosynthesis [73]. The ellagitannins can then be hydrolyzed to ellagic acid (22), and subsequently converted to urolithins (23–27). In microorganisms the PKS-derived origin was independently postulated for numerous compounds. The polyketide biosynthesis has much in common with fatty acid

Streptopyridines, volatile pyridine alkaloids produced by Streptomyces sp. FORM5

• Ulrike Groenhagen,
• Michael Maczka,
• Jeroen S. Dickschat and
• Stefan Schulz

Beilstein J. Org. Chem. 2014, 10, 1421–1432, doi:10.3762/bjoc.10.146

• . Keywords: headspace analysis; natural products; polyketide biosynthesis; pyridine derivatives; streptazolin; volatile compounds; Introduction Actinomycetes are excellent producers of diverse and bioactive secondary metabolites. These metabolites belong to many different structural classes including

Synthesis of complex intermediates for the study of a dehydratase from borrelidin biosynthesis

• Frank Hahn,
• Nadine Kandziora,
• Steffen Friedrich and
• Peter F. Leadlay

Beilstein J. Org. Chem. 2014, 10, 634–640, doi:10.3762/bjoc.10.55

• polyketide-derived thioesters suited for biosynthesis studies. Keywords: aldol reaction; coenzyme A; natural products; pig liver esterase; polyketide biosynthesis; protection groups; Introduction Borrelidin (1) is a macrolactone polyketide natural product with promising antibacterial, antimalarial

Quantification of N-acetylcysteamine activated methylmalonate incorporation into polyketide biosynthesis

• Stephan Klopries,
• Uschi Sundermann and
• Frank Schulz

Beilstein J. Org. Chem. 2013, 9, 664–674, doi:10.3762/bjoc.9.75

• statement on the intracellular concentration of the artificial building block can be made. The incorporation of non-native biosynthetic building blocks into polyketide biosynthesis is an emerging field of research and requires either the elaborated engineered biosynthesis of such a building block in the

Novel fatty acid methyl esters from the actinomycete Micromonospora aurantiaca

• Jeroen S. Dickschat,
• Hilke Bruns and
• Ramona Riclea

Beilstein J. Org. Chem. 2011, 7, 1697–1712, doi:10.3762/bjoc.7.200

• elongation units, and occur due to the logic of FA biosynthesis in even-numbered positions of the FA carbon chain. An alternative mechanism leading to the same methyl branching pattern is well-known from polyketide biosynthesis and involves the incorporation of a malonyl-CoA unit followed by SAM-dependent