Synthesis and Facile Dearomatization of Highly Electrophilic Nitroisoxazolo[4,3-b]pyridines

A number of novel 6-R-isoxazolo[4,3-b]pyridines were synthesized and their reactions with neutral C-nucleophiles (1,3-dicarbonyl compounds, π-excessive (het)arenes, dienes) were studied. The reaction rate was found to be dependent on the nature of the substituent 6-R. The most reactive 6-nitroisoxazolo[4,3-b]pyridines are able to add C-nucleophiles in the absence of a base under mild conditions. In addition, these compounds readily undergo [4+2]-cycloaddition reactions on aromatic bonds C=C(NO(2)) of the pyridine ring, thus indicating the superelectrophilic nature of 6-NO(2)-isoxazolo[4,3-b]pyridines.