Versatile synthetic routes are described for the preparation of a range of epoxyquinol and epoxyquinone analogues of the antitumour antibiotic manumycin A lacking the lower side chain, and these procedures have also been applied to prepare the bioactive natural product LL-C10037a. The extension of this methodology to provide a general synthetic route to the manumycin family of antibiotics is discussed and exemplified by the first total synthesis of alisamycin and ent-alisamycin. This route includes the novel, stereoselective organometallic addition of the Corey-Wollenberg reagent (E-2-tributylstannylethenyllithium) to the manumycin nucleus and palladium catalysed Stille coupling technology for the introduction of the polyunsaturated 2-amino-3hydroxycyclopentenone derived amide. Similar methodology has also been employed to complete the first total synthesis of the antibiotic nisamycin.

The Synthesis of Alisamycin, Nisamycin, LL-C10037α and Novel Epoxyquinol and Epoxyquinone Analogues of Manumycin A -[ca. 50 refs.] -(TAYLOR, R. J. K.; ALCARAZ, L.; KAPFER-EYER, I.; MACDONALD, G.; WEI, X.; LEWIS, N.; Synthesis (1998) 5, 775-790; Dep. Chem., Univ. York, Heslington, York YO10 5DD, UK; EN)