synthetic studies towards the ent-labdane diterpenoids rearrangement of ent-halimanes合成研究向ent-labdane二萜ent-halimanes重排.pdfVIP

Molecules 2006, 11, 792-807 molecules ISSN 1420-3049 Full Paper Synthetic Studies Towards the ent-Labdane Diterpenoids: Rearrangement of ent-Halimanes * Isidro S. Marcos , María J. Sexmero, Felix A. Hernández, Marta Corrales, Pilar Basabe, David Díez and Julio G. Urones Departamento de Química Orgánica, Universidad de Salamanca, Plaza de los Caídos 1-5, 37008 Salamanca, Spain * Author to whom correspondence should be addressed; E-mail: ismarcos@usal.es Received: 29 September 2006; in revised form: 18 October 2006 / Accepted: 23 October 2006 / Published: 24 October 2006 Abstract: For the first time ent-labdanes have been synthetised starting from ent-halimic acid, following a route that is the reverse of the biosynthetic one leading to the former compounds. Keywords: Rearrangement, ent-labdanes, ent-halimic acid. Introduction ent-Halimic acid (Figure 1) is a bicyclic diterpene that has been used as a starting material for the synthesis of different bioactive molecules such as the ent-halimanolides [1], chettaphanin I and chettaphanin II [2], (+)-agelasine C [3] and sesterterpenolides with an disydiolane skeleton [4]. Due to its functionality, ent-halimic acid can be viewed as an excellent synthon for the synthesis of new natural products. For example, the bicyclic system of ent-halimic acid can be visualized as the basis for the BC rings of tricyclic diterpenes or quassinoids with a picrasane skeleton (Scheme 1) whereby the C-4 quaternary carbon and the C-5 carbon of the starting material are incorporated with the correct configuration as C-10 and C