@article{pittir25623, volume = {64}, number = {14}, month = {July}, author = {P Wipf and PDG Coish}, title = {Total synthesis of ({$\pm$})-nisamycin}, journal = {Journal of Organic Chemistry}, pages = {5053 -- 5061}, year = {1999}, url = {http://d-scholarship-dev.library.pitt.edu/25623/}, abstract = {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.} }