Part I. Aromatic annelation: Synthesis of naphthalenes. Part II. C-glycosyl anthraquinone synthesis: Total synthesis of vineomycinone B2 methyl ester

art one. A synthesis of naphthalenes by an aromatic annelation sequence is described. ;Several naphthalenes were prepared by this sequence, and the potential of the sequence is illustrated by the synthesis of a phenanthrene.;Part two. The synthesis of functionalized hydroxyanthraquinones is reported. The method utilized was applied to a total synthesis of vineomycinone B2 methyl ester, the aglycone of the C-glycosyl anthraquinone antibiotic vineomycin B2.;Hydroxyanthraquinones were protected as the corresponding methoxymethyl ethers and reduced to the antracenes with sodium borohydride in refluxing isopropanol. These anthracenes could be cleanly lithiated and functionalized by reaction with reactive electrophiles. The lithio derivatives could also be captured by stannylation and the stannanes iodinated. These iodoanthracenes underwent Pd-catalyzed coupling reactions to generate the corresponding C-C bonds in a highly regiospecific manner.;The use of a protected glucal derivative generated from the commercially available tri-O-acetyl-D-glucal afforded a C-glycosyl anthracene. Hydrogenation with sodium cyanoborohydride in methanolic HCl generated the corresponding...