Discovery and biosynthesis of bacterial drimane-type sesquiterpenoids from Streptomyces clavuligerus

• Dongxu Zhang,
• Wenyu Du,
• Xingming Pan,
• Xiaoxu Lin,
• Fang-Ru Li,
• Qingling Wang,
• Qian Yang,
• Hui-Min Xu and
• Liao-Bin Dong

Beilstein J. Org. Chem. 2024, 20, 815–822, doi:10.3762/bjoc.20.73

• with literature data [29]. This marks the first discovery of natural DMTs from bacteria, surpassing previous findings of bacterial DMSs which focused only on the enzyme itself without reporting natural DMT or exploring associated BGCs [17]. Additionally, while drimentines, bacterial meroterpenoids

• findings from both the heterologous expression and substrate spectrum analysis indicate the particular affinity of CavA for the C-3 position, which might be used for chemoenzymatic synthesis of C-3 hydroxylated drimanyl meroterpenoids using drimenol and its analogues as substrates. However, it is important

Production of non-natural 5-methylorsellinate-derived meroterpenoids in Aspergillus oryzae

• Jia Tang,
• Yixiang Zhang and
• Yudai Matsuda

Beilstein J. Org. Chem. 2024, 20, 638–644, doi:10.3762/bjoc.20.56

• Jia Tang Yixiang Zhang Yudai Matsuda Department of Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong SAR, China 10.3762/bjoc.20.56 Abstract Fungal meroterpenoids are diverse structurally intriguing molecules with various biological properties. One large group within

• this compound class is derived from the aromatic precursor 3,5-dimethylorsellinic acid (DMOA). In this study, we constructed engineered metabolic pathways in the fungus Aspergillus oryzae to expand the molecular diversity of meroterpenoids. We employed the 5-methylorsellinic acid (5-MOA) synthase FncE

• , demonstrating the effectiveness of our approach in the generation of structural analogues of meroterpenoids. Keywords: biosynthesis; meroterpenoids; natural products; pathway engineering; terpene cyclases; Introduction Meroterpenoids are a class of natural products partially biosynthesized from a terpenoid

Recent developments in the engineered biosynthesis of fungal meroterpenoids

• Zhiyang Quan and
• Takayoshi Awakawa

Beilstein J. Org. Chem. 2024, 20, 578–588, doi:10.3762/bjoc.20.50

• Zhiyang Quan Takayoshi Awakawa RIKEN Center for Sustainable Resource Science, Wako, Saitama 351-0198, Japan 10.3762/bjoc.20.50 Abstract Meroterpenoids are hybrid compounds that are partially derived from terpenoids. This group of natural products displays large structural diversity, and many

• for the design of biosynthetic machineries to produce a variety of bioactive meroterpenoids. Keywords: αKG-dependent dioxygenases; enzyme engineering; fungal meroterpenoids; synthetic biology; terpene cyclases; Introduction Meroterpenoids are complex natural products with intricate skeletal

• structures, and are partially derived from terpenoids [1]. Many fungal meroterpenoids are composed of polyketide and terpenoid moieties. Examples of fungal meroterpenoids include mycophenolic acid (Figure 1, 1), which shows immunosuppressive activity and cell differentiation-inducing activity by inhibiting

Pseudallenes A and B, new sulfur-containing ovalicin sesquiterpenoid derivatives with antimicrobial activity from the deep-sea cold seep sediment-derived fungus Pseudallescheria boydii CS-793

• Zhen Ying,
• Xiao-Ming Li,
• Sui-Qun Yang,
• Hong-Lei Li,
• Xin Li,
• Bin-Gui Wang and
• Ling-Hong Meng

Beilstein J. Org. Chem. 2024, 20, 470–478, doi:10.3762/bjoc.20.42

• our attention. Several meroterpenoids, alkaloids, polyketides, and sesquiterpenoids from the species displayed various biological properties including anti-inflammatory, antimicrobial, and cytotoxic activities [7][8][9]. In the present work, two rare new examples of sulfur-containing ovalicin

Combining the best of both worlds: radical-based divergent total synthesis

• Kyriaki Gennaiou,
• Antonios Kelesidis,
• Maria Kourgiantaki and
• Alexandros L. Zografos

Beilstein J. Org. Chem. 2023, 19, 1–26, doi:10.3762/bjoc.19.1

• coupling to 13, 20, 25, and 28, few steps away from the total syntheses of sesquicillin A (18), subglutinols A and B (19 and 24) and higginsianin A (23, Scheme 2). Merged chemoenzymatic and radical synthesis of oxidized pyrone meroterpenoids (Renata 2020) [29]: In 2020, a different approach was

• conceptualized by Renata’s group to access various oxidized members of pyrone meroterpenoids. The divergent plan of Renata’s group depended on the development of a highly chemoselective, chemoenzymatic 3-hydroxylation of sclareolide (29) and (−)-sclareol (43, Scheme 3 and Scheme 4). The group began by conducting

• pyrone meroterpenoids on sclareolide (29). Key reaction of this strategy was the formal [3 + 3] cycloaddition, catalyzed by phosphoric acid 33, followed by addition of a pyrone residue 32 to sclareolide-derived aldehyde 31, which served as the common synthetic intermediate for the synthesis (Scheme 3

Identification of the new prenyltransferase Ubi-297 from marine bacteria and elucidation of its substrate specificity

• Jamshid Amiri Moghaddam,
• Huijuan Guo,
• Karsten Willing,
• Thomas Wichard and
• Christine Beemelmanns

Beilstein J. Org. Chem. 2022, 18, 722–731, doi:10.3762/bjoc.18.72

• , we aimed to gain insights into abundance and diversity of Ptases encoded in both, Flavobacteria and members of the Phylum Actinobacteria, as these were suggested to be involved in the production of meroterpenoids [2]. Thus, the genomes of marine Flavobacteria, including members of the genera

α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions

• Scott Benz and
• Andrew S. Murkin

Beilstein J. Org. Chem. 2021, 17, 2570–2584, doi:10.3762/bjoc.17.172

• that further studies of this type of rearrangement in a biological system are currently being attempted. As a final example of natural products believed to form as a result of an α-ketol rearrangement, Li et al. isolated and characterized eight novel acylphloroglucinol meroterpenoids, known as

Natural products in the predatory defence of the filamentous fungal pathogen Aspergillus fumigatus

• Jana M. Boysen,
• Nauman Saeed and
• Falk Hillmann

Beilstein J. Org. Chem. 2021, 17, 1814–1827, doi:10.3762/bjoc.17.124

• region on chromosome 6 [172]. Chemically, pyripyropene (PP) analogs are meroterpenoids containing a fused pyridyl α-pyrone moiety and eight contiguous stereocenters [170]. Metabolically, PPPA non-covalently binds within the fifth transmembrane domain of acyl-coenzyme A (CoA):cholesterol acyltransferase

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

• ], triterpenoids [10] and prenylated polyketide meroterpenoids [11][12][13][14][15] isolated from soil, endophytes and marine strains. Of this genus, A. ustus [16], A. calidoustus [17], A. insuetus [17], A. insulicola [18], A. bridgeri [18], A. sclerotiorum [19], A. variecolor [19], A. parasiticus [20], A. oryzae

Synthesis of acremines A, B and F and studies on the bisacremines

• Nils Winter and
• Dirk Trauner

Beilstein J. Org. Chem. 2019, 15, 2271–2276, doi:10.3762/bjoc.15.219

• Nils Winter Dirk Trauner Department of Chemistry, University of Munich, Butenandtstraße 5–13, 81377 Munich, Germany Department of Chemistry, New York University, 100 Washington Square East, Room 712, New York, NY 10003, USA 10.3762/bjoc.15.219 Abstract The acremines are a family of meroterpenoids

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

• . This motif is found in its intact or modified form in indolocarbazoles, macrocyclic polyketides (cytochalasan alkaloids), the aporhoeadane alkaloids, meroterpenoids from Stachybotrys species and anthraquinone-type alkaloids. Concerning their biological activity, molecular structure and synthesis, we

• copper(II) triflate-catalyzed Ullmann coupling furnished 136. Meroterpenoids: The term meroterpenoids describes a family of natural products with a mixed biosynthetic origin, partially derived from terpenoids and polyketides [129]. Several members of this class containing an isoindolinone motif, for

• erinaceum [137][138]. Another member of this family, aspernidine A (164), was recently isolated form the fungus Aspergillus nidulans by Hertweck [139]. A comprehensive review about meroterpenoids produced by fungi was published by Simpson in 2009 [140]. The isolated molecules display a broad spectrum of