[3 + 2] Cycloaddition of nitrile oxides to dichloropropenes and 1,3‐dichlorobut‐2‐ene: A regioselectivity issue

Abstract

The reaction of nitrile oxides with 2,3‐dichloroprop‐1‐ene, 1,3‐dichloroprop‐1‐ene, and 1,3‐dichlorobut‐2‐ene leads to 5‐(chloromethyl)isoxazoles, 4‐(chloromethyl)isoxazoles, or to mixtures of both regioisomers. The direction of cycloaddition and reactivity of substrate is determined by the steric hindrance at the terminal carbon atom of the alkene double bond. It has been found that the isomeric products of cycloaddition of nitrile oxides to 1,3‐dichloropropene have significantly different dehydrochlorination capabilities. The experimental data on the regioselectivity of cycloaddition and the relative reactivity of substrates are in agreement with the results of quantum chemical calculations.