578. Transannular reactions in the caryophyllene series

Greenwood, J. M.; Qureshi, I. H.; Sutherland, J. K.

doi:10.1039/jr9650003154

Cited by 5 publications

(1 citation statement)

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“…The cleavage of diol 7 by NaIO 4 was performed to obtain compound 8, known also as the natural product kobusone. The epoxide in kobusone (8) was then isomerized to an allylic alcohol in acidic media in the presence of NaI, 10 furnishing compound 9, known also as isokobusone. 11 The structure of isokobusone (9) was confirmed by X-ray crystallography; however, it was found by NMR that ∼13% of the material exists as a cyclic hemiacetal in CDCl 3 solution (Supporting Information, Table S1).…”

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confidence: 99%

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

Stakanovs,

Blazevica,

Belyakov

et al. 2023

J. Nat. Prod.

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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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confidence: 99%