Fleming−Tamao Oxidation and Masked Hydroxyl Functionality: 
Total Synthesis of (+)-Pramanicin and Structural Elucidation of
the Antifungal Natural Product (−)-Pramanicin

G. M. Barrett, Anthony; Head, John; L. Smith, Marie; Stock, Nicholas S.; J. P. White, A.; Williams, D. J.

doi:10.1021/jo9905672.s002

jo9905672_si_002.pdf (1.03 MB)

Fleming−Tamao Oxidation and Masked Hydroxyl Functionality: Total Synthesis of (+)-Pramanicin and Structural Elucidation of the Antifungal Natural Product (−)-Pramanicin

journal contribution

posted on 1999-07-23, 00:00 authored by Anthony G. M. Barrett, John Head, Marie L. Smith, Nicholas S. Stock, A. J. P. White, D. J. Williams

The total synthesis of (+)-pramanicin (41b) is reported, thereby establishing the relative and absolute stereochemistry of the naturally occurring antifungal agent. The key steps involve (i) conjugate addition of the diethyl((diethylamino)diphenylsilyl)zincate to a suitably protected γ-lactam 3 and quenching of the resultant enolate with the α,β-unsaturated γ,δ-epoxy aldehyde 2 (X = H), (ii) Ni(acac)₂-catalyzed hydroxylation of a β-dicarbonyl array, and (iii) Fleming−Tamao oxidation to reveal the masked C-3 hydroxyl group.