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Total Synthesis of Brasilicardins A and C
Masahiro Anada1, Taiki Hanari1, Kosuke Kakita1
1Faculty of Pharmaceutical Sciences, Hokkaido University , Sapporo 060-0812, Japan.
Abstract:
The first total synthesis of brasilicardins A and C, novel diterpenoid-saccharide-amino acid hybrid metabolites with unique immunosuppressive activity, is described. The key step is a Diels-Alder/reductive angular methylation sequence capitalizing on a trans-fused bicyclic α-cyano-α,β-enone as its precursor to construct the 8,10-dimethyl-trans/syn/trans-perhydrophenanthrene skeleton. Other notable features include an anti-selective aldol reaction, a stereocontrolled glycosylation of a C2 alcohol, and a one-pot, two-step global deprotection sequence that did not damage these sensitive molecules.
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