Rh(II)/Mg(O^<i>t</i>Bu)₂-Catalyzed Tandem One-Pot Synthesis of 1,4-Oxazepines and 1,4-Oxazines from <i>N</i>-Sulfonyl-1,2,3-triazoles and Glycidols

Abstract

A novel, one-pot route for the synthesis of nonaromatic ring-fused 1,4-oxazepines and 1,4-oxazines has been developed. The reaction features a sequential rhodium(II)-catalyzed reaction of N -sulfonyl-1,2,3-triazoles with glycidols, followed by a regioselective Lewis acid Mg(O t Bu) 2 -catalyzed intramolecular ring-opening reaction. It has been found that the regioselectivity in the epoxide ring-opening was largely determined by the substituents on the glycidols. Thus, substituted glycidols (R 2 ≠ H) afforded seven-membered oxazepine derivatives selectively, while unsubstituted glycidols (R 2 = H) afforded six-membered oxazine derivatives. Plausible reaction pathways are elucidated and supported by experiments with several glycidols bearing different substituents around the epoxide functionality.