Dept. of Chemistry
Oregon Graduate Center
Olivin is the aglycone of olivomycin, a naturally occurring anti-tumor antibiotic. Synthesis of the aromatic portion of olivin was accomplished by using a new annellation procedure whereby 3-methyl- 6, 8-dimethoxy-1H-2-benzopyran-1-one was condensed with the lithium enolate of ethyl acetate to yield ethyl 1-hydroxy-6, 8-dimethoxy-3- methyl-2-naphthoate. The ortho relationship of the methyl and carboethoxy groups in the naphthoate was exploited in building the non-aromatic ring of olivine. Cycloaddition of maleic anhydride to dienes generated photochemically from 2-methylnaphthoyl nitriles failed. Base promoted condensation of triethyl 1, 1, 2-ethanetricarboxylate with ethyl 5(or 7)-bromo-1, 6, 8- trimethoxy-3-bromomethyl-2-naphthoate, generated the tricyclic anthracenone skeleton characteristic of olivine However, the subsequent steps of hydrolysis and decarboxylation were not successful. The introduction of the side-chain was effected on a model substrate through the use of the lithium enolate of 2-propylidene-1, 3-dithiane as a nucleophilic "acyl anion" equivalent.
Pogany, Stefano Andrea, "A synthetic approach to olivin" (1978). Scholar Archive. 62.