| Abstract
| - 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 intermediate14. Compound 14 was prepared in five synthetic steps from (+)-podocarp-8(14)-en-13-one 13, easilyavailable from commercial (−)-abietic acid. The key steps in the syntheses were a regioselectivereduction 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 presentsan unprecedented δ-lactone-based structure for spongiane-type diterpenoids. A theoretical studyincluding a series of ab initio calculations for the mechanism involved in the conversion of ester 22into natural product 2 has also been carried out.
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