Oxidative Degradations of the Side Chain of Unsaturated Ent-labdanes. Part I. 英文参考文献.docVIP

Molecules 2007, 12, 318-327 molecules ISSN 1420-3049 Full Paper Oxidative Degradations of the Side Chain of Unsaturated Ent-labdanes. Part I. Luis Espinoza Catalán 1,*, Héctor Carrasco Altamirano 2, Mauricio Cuellar Fritis 3, Claudio Gallardo Araya 1 and Karen Catalán Marín 1 1 Departamento de Química, Universidad Técnica Federico Santa María, Av. Espa?a N° 1680, Valparaíso, Chile 2 Departamento de Ciencias Químicas, Universidad Andrés Bello, Campus Vi?a del Mar, Los Fresnos N° 52, Vi?a del Mar, Chile 3 Facultad de Farmacia, Universidad de Valparaíso, Av. Gran Breta?a N° 1093, Valparaíso, Chile * Author to whom correspondence should be addressed; E-mail: luis.espinozac@usm.cl Received: 22 November 2006; in revised form: 19 January 2007 / Accepted: 24 January 2007 / Published: 6 March 2007 Abstract: A selective route for the degradation of the unsaturated side chain of ent-labdanes has been devised, giving two useful synthons: 2β-acetoxy-14,15,17-trinor-ent-labdane-8,13- dione (5) and 2β-acetoxy-14,15-dinor-ent-labd-8(17)-en-13-one (7), the use of which for the preparation of terpenylquinone derivatives shall be reported elsewhere. Keywords: Ent-labdanes, selective degradations, unsaturated side chain. Introduction Diterpenoids with labdanic structures are a very important natural source of hydrocarbon skeletons which have been used in the elaboration of a great number of drimane compounds with remarkable biological properties, among which their olfactory [1-3], antifeedant [4], antimicrobial, cytotoxic [5], growth regulator [6], herbicidal and insecticidal activities [7-10] may be mentioned. The more common templates used for semisynthetic work are tricyclic diterpenoids such as (+)-abietic acid, (-)-levopimaric acid, podocarpic acid and bicyclic diterpenoids like manool, the communic acids, (-)-sclareol, (+)-cis-abienol, labdanolic acid, glycirretinic acid [11] and zamoranic acid [12-13]. Oxidative cleavage r