Preparation and photochemical rearrangements of 2-phenyl-2,5-cyclohexadien-1-ones. an efficient route to highly substituted phenols

Abstract

[reaction: see text]. The synthesis of 2-phenyl-2,5-cyclohexadien-1-ones 1a-c and 2a-b from methyl 3-phenylbenzoate 4 and methyl 2-methoxy-5-phenylbenzoate 8 by the Birch reduction alkylation methodology is described. 1a-c and 2a-b undergo regiospecific photorearrangements at 300 nm to give tetrasubstituted phenols 14a-c and pentasubstituted phenols 18a-b, respectively. The type A photoproducts 17a-b resulting from irradiation of 2a-b at 366 nm have been isolated as approximately 1:1 diastereomer mixtures. When an optimized condition is applied, a single diastereomer of 17a is obtained.