Biomimetic Enantioselective Total Synthesis of (−)-Robustanoids A and B and Analogues

We report a step-economical, enantioselective
total synthesis of
(−)-robustanoid B and (−)-robustanoid A and four novel
natural product-like compounds. Our strategy relied on our biosynthetic
hypothesis and on a novel complexity generation methodology, namely,
the one-pot hydroxylative double cyclization reaction. The latter
consists of a modified 3,3-dimethyldioxirane-triggered epoxidationepoxide-ring-opening
cyclization reaction cascade and Trost’s regioselectivity umpolung
methodology (“anti-Michael addition”).