Latvian Institute of Organic Synthesis, Aizkraukles 21, Riga LV-1006, Latvia.
J Nat Prod. 2023 Oct 27;86(10):2368-2378. doi: 10.1021/acs.jnatprod.3c00574. Epub 2023 Oct 1.
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.
本文介绍了陆地抗炎天然产物土木香烯 A-C 的首个半合成途径和海洋天然产物鲁蓬内酯 H 的改良合成途径。在所合成的目标化合物中，土木香烯 A 的正确结构被确定为最初提出的结构的非对映异构体，其中二级醇的立体中心倒置。土木香烯 B 和鲁蓬内酯 H 的提出结构得到了确认。然而，土木香烯 C 的正确结构被发现是最初提出的结构的非对映异构体，其中环氧部分的叔碳原子的立体中心倒置。土木香烯 A-C 和鲁蓬内酯 H 的结构通过单晶 X 射线衍射法得到了明确的确认。这些结果使上述天然产物的生物合成起源得到了明确，并增加了可用倍半萜的多样性。土木香烯 A-C 和鲁蓬内酯 H 已获得足够的量，可进一步扩展其生物活性谱，并作为未来陆地和海洋生物化学成分研究的参考标准。
