Useful Extensions of the Henry Reaction: Expeditious Routes to Nitroalkanes and Nitroalkenes in Aqueous Media

Abstract

The products of the Henry nitroaldol reaction from nitromethane and several aldehydes were reduced to the corresponding nitroalkanes with (n-Bu)₃SnH in water under microwave irradiation (80 °C/10 min), or dehydrated to the corresponding nitroalkenes with K₂CO₃ in water (generally 0–5 °C/20 min). Both “one-pot” reactions occur in excellent yields across a range of aliphatic and aromatic (including heteroaromatic) substrates. It seems likely that the deoxygenation of the nitroaldols occurs via coordination of an oxygen atom of the nitro group with a tin atom, which facilitates hydride delivery in the transition state. The elimination of water from the nitroaldols in mild base is likely driven by the stability of the conjugated nitroalkene products. The elimination required workup with 2 N HCl, which likely displaces a nitroalkane-nitroalkene equilibrium towards the latter. These extensions of the Henry reaction lead to products not easily obtained otherwise.

GRAPHICAL ABSTRACT

Keywords:

• Aldol
• aqueous conditions
• dehydration
• deoxygenation
• Henry
• nitromethane
• tin hydride