The first total synthesis of lajollamycin B, as tructurally novel nitro-tetraene spiro-b-lactone/g-lactonea ntibiotic, is described. The convergent synthesis involves the construction of the C8'-C11' nitrodienylstannane and its coupling with the segment prepared from the C1'-C7' w-iodo-heptadienoic acid and the right-hand heterocyclic fragment, which has been utilized for our previouss yntheses of oxazo-lomycinA.T he revisiono ft he geometry of the terminal D 10',11' -double bond from E to Z is also described for the structure of natural lajollamycin B.

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.