Electrosynthesis of benzyl-tert-butylamine via nickel-catalyzed oxidation of benzyl alcohol†

Abstract

The development of sustainable synthetic methods for converting alcohols to amines is of great interest due to their widespread use in pharmaceuticals and fine chemicals. In this work, we present an electrochemical approach by using green electrons for the selective oxidation of benzyl alcohol to benzaldehyde using a NiOOH catalyst, followed by its reductive amination to form benzyl-tert-butylamine. The number of Ni monolayer equivalents on the catalyst was found to significantly influence selectivity, with 2 monolayers achieving up to 90% faradaic efficiency (FE) for benzaldehyde in NaOH, while 10 monolayers performed best in a tert-butylamine solution (pH 11), yielding 100% FE for benzaldehyde. Reductive amination of benzaldehyde was optimized on Ag and Pb electrodes, with Ag achieving 39% FE towards the amine product, though hydrogen evolution remained a competing reaction. In situ FTIR spectroscopy confirmed the formation of benzaldehyde and its corresponding imine intermediate during oxidation, while reduction spectra supported the formation of the amine product. These results demonstrate the potential of paired electrolysis for alcohol-to-amine conversion, achieving an overall 35% FE for the synthesis of benzyl-tert-butylamine. This work paves the way for more efficient and sustainable electrochemical routes to amine synthesis.