An enantiospecific approach to tricyclic sesquiterpenes mayurone and thujopsenes.
An enantiospecific approach to mayurone and thujopsenes, sesquiterpenes containing three contiguous quaternary carbon atoms, starting from (R)-carvone (8), is described. (S)-3,4,4-Trimethylcarvone (7), obtained from (R)-carvone, was transformed into the bicyclo[2.2.2]octanone 13 via regioselective intramolecular alkylation of the allyl bromide 11. Regioselective ozonolysis and Criegee fragmentation of the bicyclic ketone 13 furnished the keto ester 14. Reductive deoxygenation followed by one-carbon homologation transformed the keto ester 19 into the ester 6. Intramolecular cyclopropanation of the diazo ketone 25, derived from the acid 5, furnished (-)-dihydromayurone (4), thus constituting a formal enantiospecific synthesis of mayurone and thujopsenes.
Srikrishna
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Department of Organic Chemistry, Indian Institute of Science, Bangalore 560 012, India. ask@orgchem.iisc.ernet.in
Anebouselvy
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D000972:Antineoplastic Agents, Phytogenic / Q000737:chemistry; D029779:Cupressaceae / Q000737:chemistry; D000081005:Cyclohexane Monoterpenes; D039821:Monoterpenes; D010938:Plant Oils / Q000737:chemistry; D000081223:Polycyclic Sesquiterpenes; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013729:Terpenes / Q000737:chemistry
D000972:Antineoplastic Agents, Phytogenic; D000081005:Cyclohexane Monoterpenes; D039821:Monoterpenes; D010938:Plant Oils; D000081223:Polycyclic Sesquiterpenes; D012717:Sesquiterpenes; D013729:Terpenes; C433909:mayurone; C006923:carvone; C433908:thujopsene