Easy access to a cyclic key intermediate for the synthesis of trisporic acids and related compounds.
The synthesis of a cyclohexane skeleton possessing different oxygenated functional groups at C-3, C-8 and C-9, and a D1,6-double bond has been accomplished in 10 steps with an overall 17% yield. This compound is a key intermediate for access to a wide range of compounds of the bioactive trisporoid family. The synthetic sequence consists of the preparation of a properly functionalized epoxygeraniol derivative, and its subsequent stereoselective cyclization mediated by Ti(III). This last step implies a domino process that starts with a homolytic epoxide opening followed by a radical cyclization and regioselective elimination. This concerted process gives access to the cyclohexane moiety with stereochemical control of five of its six carbon atoms.
Department of Organic Chemistry and Institute of Biotechnology, University of Granada, Avda Fuentenueva s/n, 18071 Granada, Spain.
José A
JA
González-Delgado
Department of Organic Chemistry and Institute of Biotechnology, University of Granada, Avda Fuentenueva s/n, 18071 Granada, Spain.
Gustavo
G
Escobar
CIQSO-Center for Research in Sustainable Chemistry and Department of Chemical Engineering, Physical Chemistry and Organic Chemistry, University of Huelva, Avda 3 Marzo s/n, 21071 Huelva, Spain. jesus.fernandez@diq.uhu.es.
Jesús F
JF
Arteaga
Department of Organic Chemistry and Institute of Biotechnology, University of Granada, Avda Fuentenueva s/n, 18071 Granada, Spain. afbarre@ugr.es.
Alejandro F
AF
Barrero
D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D003510:Cyclohexanes / Q000737:chemistry; D004852:Epoxy Compounds / Q000737:chemistry*; D005231:Fatty Acids, Unsaturated / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
D003510:Cyclohexanes; D004852:Epoxy Compounds; D005231:Fatty Acids, Unsaturated; C004574:trisporic acid; C506365:Cyclohexane; D002244:Carbon