Organic & Biomolecular Chemistry 2012-10-14

The synthesis of the pyranonaphthoquinones dehydroherbarin and anhydrofusarubin using Wacker oxidation methodology as a key step and other unexpected oxidation reactions with ceric ammonium nitrate and salcomine.

Adushan Pillay, Amanda L Rousseau, Manuel A Fernandes, Charles B de Koning

Index: Org. Biomol. Chem. 10(38) , 7809-19, (2012)

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Abstract

The synthesis of two closely related pyranonaphthoquinones, dehydroherbarin and anhydrofusarubin, is described. The construction of the naphthalene nuclei was achieved using the Stobbe condensation reaction using 2,4-dimethoxybenzaldehyde and 2,4,5-trimethoxybenzaldehyde as their respective starting materials. Two key steps en route include a PIFA-mediated addition of a methoxy substituent onto the naphthalene skeleton and a Wacker oxidation reaction to construct the benzo[g]isochromene nucleus. Two interesting oxidation reactions of the intermediate isochromene enol ether of 7,9-dimethoxy-3-methyl-1H-benzo[g]isochromene-5-ol were observed. Treatment of the substrate with salcomine resulted in the formation of (3-formyl-4-hydroxy-6,8-dimethoxynaphthalene-2-yl)methyl acetate, while treatment of the same substrate with CAN resulted in the formation of racemic (3R,4R)-3-hydroxy-7,9-dimethoxy-3-methyl-5,10-dioxo-3,4,5,10-tetrahydro-1H-benzo[g]isochromen-4-yl nitrate.