3-Halo-5,6-dihydro-4H-1,2-oxazine N-oxides as synthetic equivalents of unsaturated nitrile oxides in the [3 + 2]-cycloaddition with arynes: synthesis of substituted 3-vinyl-1,2-benzisoxazoles.

Abstract

The reaction of 3-halo-5,6-dihydro-4H-1,2-oxazine N-oxides with arynes was studied. Arynes were generated from o-silylaryl triflates and underwent consecutive [3 + 2]-cycloaddition/[4 + 2]-cycloreversion with N-oxides leading to substituted 3-vinyl-benzisoxazoles in high yields. In the presented sequence, 1,2-oxazine N-oxides act as surrogates of rarely employed unsaturated nitrile oxides. A broad substrate scope was demonstrated. The influence of the substitution pattern of an aryne on the reaction outcome was determined. In the presence of bulky substituents, polycyclic 4,4a-dihydro-3H-benzofuro[3,2-c][1,2]oxazines were selectively formed. Mechanistic schemes for the observed reaction pathways were proposed. The synthetic utility of the products was demonstrated by their follow-up modifications.