The asymmetric total synthesis of (+)-marinomycin A, a 44-membered macrodiolide antitumor agent and antibiotic isolated from a marine actinomycete, Marinispora strain CNQ-140, is reported. The key features of the synthesis include the highly convergent stereocontrolled construction of the monomeric hydroxy salicylate starting from asymmetric epoxidation of the σ-symmetrical dialkenyl carbinol, and an unprecedented direct dimerization through NaHMDS-promoted double transesterification.

The asymmetric total synthesis of (+)-marinomycin A, a 44-membered macrodiolide antitumor agent and antibiotic isolated from a marine actinomycete, Marinispora strain CNQ-140, is reported. The key features of the synthesis include the highly convergent stereocontrolled construction of the monomeric hydroxy salicylate starting from asymmetric epoxidation of the s-symmetrical dialkenyl carbinol, and an unprecedented direct dimerization through NaHMDS-promoted double transesterification.

Total Synthesis of Marinomycin A Based on a Direct Dimerization Strategy. -(NISHIMARU, T.; KONDO, M.; TAKESHITA, K.; TAKAHASHI, K.; ISHIHARA, J.; HATAKEYAMA*, S.; Angew. Chem., Int. Ed. 53 (2014) 32, 8459-8462, http://dx.