Construction of the Pentacyclic Core and Formal Total Synthesis of (rac)-Renieramycin T

A formal total synthesis of the antitumor marine natural product (rac)-renieramycin T, which possesses a characteristic ecteinascidin-type A ring in the renieramycin-saframycin core skeleton, was elaborated. The key steps in the synthesis of (rac)-renieramycin T are a modified Pictet-Spengler cyclization of dialkylated oxomalonate derivatives and decarboxylation via a monocarboxylic acid derivative followed by stereocontrolled protonation of the enol intermediate. A key intermediate in our previous synthesis of renieramycin T was used, and the formal synthesis was accomplished in 21 steps from a known piperazine-2,5-dione derivative.