Allylic Nitro Compounds as Nitrite Donors

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Abstract
Allylic nitro compounds were synthesized and evaluated as organic sources of nitrite and nitric oxide. Unactivated allylic nitro compounds do not spontaneously release nitrite and nucleophile promoted nitrite release is slow. However, 2-(nitromethyl)-cyclohex-1-ene-3-one spontaneously dissociates in buffer (pH = 7.4) to release nitrite with a kobs = 1.6 × 10-5 s-1. In the presence of l-cysteine, this compound rapidly yields nitrite and reacts with hemoglobin similarly to sodium nitrite. Structural modifications and the nature and amount of nucleophile modulate the rate of nitrite release. In the presence of l-cysteine and ascorbic acid, this compound forms nitric oxide. Together, these results reveal a new structural architecture for the tunable liberation of nitrite and nitric oxide from organic compounds.