Novel ring chemistry of vitamin B6 with singlet oxygen and an activated ene: isolated products and identified intermediates suggesting an operable [3 + 2] cycloaddition.

Pyridoxine reaction with (1)O(2) in aqueous solution at neutral pH resulted in oxidation at the 2- and 6-positions of the pyridine ring and unprecedented ring contraction. Kinetic and low temperature studies provided observable intermediates by NMR spectroscopy. In addition, novel cycloaddition between pyridoxine and N-methylmaleimide, without N-alkylation and in water, suggest a common [3 + 2] cycloaddition with the 3-hydroxypyridine ring.