6533b835fe1ef96bd12a00f6
RESEARCH PRODUCT
Synthesis of C-17-functionalized spongiane diterpenes: diastereoselective synthesis of (-)-spongian-16-oxo-17-al, (-)-acetyldendrillol-1, and (-)-aplyroseol-14.
Miguel A. GonzálezRamón J. ZaragozáManuel Arnósubject
Models MolecularStereochemistryHerpesvirus 2 HumanMolecular ConformationAntineoplastic AgentsAldehydeChemical synthesisAntiviral AgentsCatalysischemistry.chemical_compoundAb initio quantum chemistry methodsTumor Cells CulturedAnimalsHumansNuclear Magnetic Resonance Biomolecularchemistry.chemical_classificationNatural productMolecular StructureOrganic ChemistryRegioselectivityStereoisomerismPhenanthrenesPoriferachemistryAbietanesIndicators and ReagentsDiterpeneDiterpenesEnoneLactoneHeLa Cellsdescription
The diastereoselective synthesis of spongiane diterpenes (-)-spongian-16-oxo-17-al 2, (-)-acetyldendrillol-1 15, and (-)-aplyroseol-14 16 has been completed efficiently via the common intermediate 14. Compound 14 was prepared in five synthetic steps from (+)-podocarp-8(14)-en-13-one 13, easily available from commercial (-)-abietic acid. The key steps in the syntheses were a regioselective reduction of a 1,4-dialdehyde unit, a one-pot acetalization-acetylation, and a translactonization. The synthesis of 15 and 16 has led us to a revision of the configuration at C-17 for natural (-)-acetyldendrillol-1 and a structural reassignment for aplyroseol-14. Thus, aplyroseol-14 16 presents an unprecedented delta-lactone-based structure for spongiane-type diterpenoids. A theoretical study including a series of ab initio calculations for the mechanism involved in the conversion of ester 22 into natural product 2 has also been carried out.
year | journal | country | edition | language |
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2003-01-10 | The Journal of organic chemistry |