A Unified Strategy for Enantioselective Total Synthesis of Cladiellin and Briarellin Diterpenes: Total Synthesis of Briarellins E and F, and the Putative Structure of Alcyonin and Revision of Its Structure Assignment

作者: Olivier Corminboeuf , Larry E. Overman , Lewis D. Pennington

DOI: 10.1021/JO9010156

关键词:

摘要: Enantioselective total syntheses of briarellin E (12) and F (13), as well the structure originally proposed for cladiellin diterpene alcyonin (10), have been realized. Comparison spectral data synthetic 10, natural alcyonin, cladiellisin (33), cladiellaperoxide (34), chemical transformations 10 suggest that this coral metabolite is allylic peroxide 11. The unified approach detailed herein can be used to access both C4-deoxygenated C4-oxygenated cladiellins briarellins. central step in these acid-promoted condensation (Z)-α,β-unsaturated aldehydes 17 with cyclohexadienyl diols 18 form intermediates 16 incorporating hexahydroisobenzofuran core five stereocenters marine diterpenes (Scheme 1).

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