Asymmetric synthesis of (+)-17-epi-methoxy-kauran-3-one through tandem oxidative polycyclization-pinacol process.
A synthesis of (+)-17-epi-methoxy-kauran-3-one, an O-methylated isomer of the natural diterpene 17-hydroxy-kauran-3-one, has been achieved. The strategy is based on a diastereoselective oxidative polycyclization-pinacol tandem process consisting of transforming a functionalized phenol into a compact and complex tetracycle, which represents the main core of kaurane family members. The synthesis also includes an enantioselective Yamamoto's allylation, a diastereoselective Ru-catalyzed hydrocyanation, a ring-closing metathesis and a reductive isomerization process as key steps. The structure of our synthetic substrate was determined through comparison with an O-methylated derivative of the natural compound.
Laboratoire de Méthodologie et Synthèse de Produits Naturels, Université du Québec à Montréal, C.P. 8888, Succ. Centre-Ville, Montréal, H3C 3P8, Québec, Canada. canesi.sylvain@uqam.ca.
Gaëtan
G
Maertens
Laboratoire de Méthodologie et Synthèse de Produits Naturels, Université du Québec à Montréal, C.P. 8888, Succ. Centre-Ville, Montréal, H3C 3P8, Québec, Canada. canesi.sylvain@uqam.ca.
Samuel
S
Desjardins
Laboratoire de Méthodologie et Synthèse de Produits Naturels, Université du Québec à Montréal, C.P. 8888, Succ. Centre-Ville, Montréal, H3C 3P8, Québec, Canada. canesi.sylvain@uqam.ca.
Sylvain
S
Canesi
D002384:Catalysis; D003500:Cyclization; D045786:Diterpenes, Kaurane / Q000138:chemical synthesis* / Q000737:chemistry; D006018:Glycols / Q000138:chemical synthesis / Q000737:chemistry*; D006865:Hydrogenation; D008745:Methylation; D010084:Oxidation-Reduction; D010636:Phenols / Q000138:chemical synthesis / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry; D013237:Stereoisomerism
D045786:Diterpenes, Kaurane; D006018:Glycols; D010636:Phenols; C000621940:pinacol; D012428:Ruthenium