Synthesis of Benzodioxepinones and Benzoxazepinones via Tandem Oxidation and Iodolactonization of 2-O/N-tethered Alkenyl Benzaldehyde Mediated by CuI/TBHP.

Abstract

An efficient methodology for the synthesis of halogenated benzodioxepinones and benzoxazecinones has been developed via tandem oxidation and iodolactonization reaction of 2-O/N-tethered alkenyl benzaldehydes mediated by CuI and tertiarybutylhydro-peroxide in acetonitrile at 70 °C in moderate to good yields. The reaction involves initial oxidation of aldehyde to acid followed by iodolactonization. Terminal propargyl ether resulted in a mixture of mono- and diiodido-3-methylene-1,4-dioxepin-5-ones. The post-synthetic modification of the reaction products leads to the formation of corresponding thiocyanate, azide, thioether, and triazole derivatives.