First total synthesis of yanuthones: Novel farnesylated epoxycyclohexenoid marine natural products

Tetrahedron Letters

Volumn 46, Issue 31, 2005, Pages 5219-5223

  Mehta, Goverdhan ^a   Pan, Subhas Chandra ^a  

^a INDIAN INSTITUTE OF SCIENCE   (India)

Author keywords

[No Author keywords available]

Indexed keywords

22 DEACYLYANUTHONE; CYCLOHEXENE DERIVATIVE; NATURAL PRODUCT; UNCLASSIFIED DRUG; YANUTHONE A; YANUTHONE B; YANUTHONE C;

ARTICLE; BIOSYNTHESIS; DRUG SYNTHESIS; STEREOCHEMISTRY;

EID: 21444439770     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2005.05.118     Document Type: Article

References (20)

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12. 13C NMR and HRMS data.
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19. The stereo- and regiochemical outcome in the DIBAL-H reduction of 18 can be rationalized in terms of the initial coordination of aluminium with the hydroxyl group and the carbonyl group as shown below. This effectively blocks the preferred exo-face, precludes additional coordination of the epoxy oxygen with DIBAL-H and activates the carbonyl group for regioselective reduction. Consequently, reduction takes place from the hindered endo-face (see arrows) of the tricyclic system to deliver the observed product 20. (Chemical presented)
20. In the case of the more flexible epoxycyclohexenone 19, the regio- and stereochemical course of the DIBAL-H reduction is directed by coordination with the epoxy oxygen and intramolecular hydride delivery from the same face, as shown below, to result in the observed stereochemistry of 21. (Chemical presented)