First synthesis of nitro-substituted 2,2-diphenyl-2 H-1-benzopyrans via the ipso-nitration reaction

Abstract

The first synthesis of a series of nitro-substituted 2,2-diphenyl-2 H-1-benzopyrans is reported. Our synthetic approach is based on a linear synthesis in two steps from appropriate brominated 2,2-diphenyl-2 H-1-benzopyrans 12– 17, which requires the preliminary preparation of bromophenols 7– 11. These latter were easily obtained by the reaction of phenols 1– 5 with a mild and selective brominating agent tetrabutylammonium tribromide (TBA·Br 3). The key intermediates 12– 17 were efficiently elaborated through an univocal classic chromenization between the commercially available 1,1-diphenyl-2-yn-1-ol and the brominated phenols 6– 11. The compounds 12– 17 so obtained were converted into arylboronic acids 18– 23 by a metalation/boronylation sequence, followed by acid hydrolysis. From advanced building blocks 18– 23, the introduction of nitro group, which constitutes the ultimate step of our strategy, was achieved by an ipso-nitration reaction using the Crivello's reagent. This highly selective method provides only the ipso-nitrated products 24– 29 in moderate to high yield.