Semisynthesis of Linariophyllenes A–C and Rumphellolide H, Structure Revisions and Proposed Biosynthesis Pathways

IF 3.3 2区生物学 Q2 CHEMISTRY, MEDICINAL

Journal of Natural Products Pub Date : 2023-10-01 DOI:10.1021/acs.jnatprod.3c00574

Georgijs Stakanovs*, Anastasija Blazevica, Sergey Belyakov, Dace Rasina and Aigars Jirgensons*,

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Abstract

The first semisynthetic routes toward terrestrial anti-inflammatory natural products linariophyllene A–C and the refined route toward marine natural product rumphellolide H are presented. Among the synthesized target compounds, the correct structure of linariophyllene A was determined to be the diastereomer of the originally proposed structure with an inverted stereocenter at the secondary alcohol. The proposed structures of linariophyllene B and rumphellolide H were confirmed. However, the correct structure of linariophyllene C was found to be the diastereomer of the originally proposed structure with an inverted stereocenter at the tertiary carbon of the epoxide moiety. The structures of linariophyllenes A–C and rumphellolide H were unequivocally confirmed by single-crystal X-ray diffractometry. The obtained results enabled the proposal of the biosynthetic origins of the aforementioned natural products and bolstered the diversity of available sesquiterpenoids. Linariophyllenes A–C and rumphellolide H were obtained in sufficient amounts to further expand their bioactivity profile and utility as reference standards in future studies of chemical constituents of terrestrial and marine organisms.

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Linariophylenes A-C和Rumphellolide H的半合成，结构修正和拟议的生物合成途径。

首次提出了陆生抗炎天然产物linariophylene A-C的半合成路线和海洋天然产物rumpellolide H的精制路线。在合成的目标化合物中，确定了正确的线性三叶烯A结构是最初提出的在仲醇处具有倒置立体中心的结构的非对映异构体。证实了所提出的芳樟醇烯B和皱皮内酯H的结构。然而，发现linariophylene C的正确结构是最初提出的结构的非对映异构体，在环氧化物部分的叔碳处具有倒置的立体中心。通过单晶X射线衍射法明确地证实了芳樟醇烯A-C和皱叶内酯H的结构。所获得的结果能够提出上述天然产物的生物合成来源，并增强了可用倍半萜的多样性。获得了足够量的Linariophylenes A-C和rumphellolide H，以进一步扩大其生物活性特征，并在未来陆地和海洋生物化学成分研究中作为参考标准。

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来源期刊

Journal of Natural Products 生物-药学

CiteScore

9.10

自引率

5.90%

发文量

294

审稿时长

2.3 months

期刊介绍： The Journal of Natural Products invites and publishes papers that make substantial and scholarly contributions to the area of natural products research. Contributions may relate to the chemistry and/or biochemistry of naturally occurring compounds or the biology of living systems from which they are obtained. Specifically, there may be articles that describe secondary metabolites of microorganisms, including antibiotics and mycotoxins; physiologically active compounds from terrestrial and marine plants and animals; biochemical studies, including biosynthesis and microbiological transformations; fermentation and plant tissue culture; the isolation, structure elucidation, and chemical synthesis of novel compounds from nature; and the pharmacology of compounds of natural origin. When new compounds are reported, manuscripts describing their biological activity are much preferred. Specifically, there may be articles that describe secondary metabolites of microorganisms, including antibiotics and mycotoxins; physiologically active compounds from terrestrial and marine plants and animals; biochemical studies, including biosynthesis and microbiological transformations; fermentation and plant tissue culture; the isolation, structure elucidation, and chemical synthesis of novel compounds from nature; and the pharmacology of compounds of natural origin.