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”).