Synthesis of geranyl phenyl ethers based on the cytotoxic monoterpenoids from the liverwort genus trichocolea

The synthesis of three geranyl ethers, methyl 4-[(2E)-3, 7-dimethyl-5-oxo-2,6-octadienyloxy]-3-methoxybenzoate (1), methyl 4-[(2E)-3,7-dimethyl-2,6-octadienyloxy]-3-methoxybenzoate (2), and methyl 4-[(2E)-3,7-dimethyl-2,6-octadienyloxy]-3-hydroxybenzoate (3), previously isolated from New Zealand Trichocolea liverworts, is described. Differing reactivity of the hydroxy groups of methyl protocatachuate toward alkylation and the ability of alkyl groups to migrate from oxygen to an ortho-oxygen in these benzene derivatives are noted.