%0 Journal Article
%@ 0022-3263
%A Wipf, P
%A Coish, PDG
%D 1999
%F pittir:25623
%J Journal of Organic Chemistry
%N 14
%P 5053 - 5061
%T Total synthesis of (±)-nisamycin
%U http://d-scholarship-dev.library.pitt.edu/25623/
%V 64
%X We have developed a highly convergent synthesis of the manumycin-type m- C7N-antibiotic nisamycin that is applicable to other members of this family of antibiotics. The synthesis features a three-step sequence to the epoxyquinol core that serves as a scaffold for the attachment of the polyene side chains. The eastern polyene side chain was constructed via a novel organozirconocene-mediated synthesis. Zirconocene methodology was also applied to the synthesis of the polyene side chains of asukamycin. The southern side chain of nisamycin was introduced via a Stille reaction that employed a vinyl bromo ketone, derived from an acid-sensitive bromo ketal. Pd-mediated coupling of the vinyl bromide with a stannyl TIPS ester gave TIPS-protected nisamycin that was readily converted to the natural product.