One-Pot Catalytic Conversion of Lignin-Derivable Guaiacols and Syringols to Cyclohexylamines

Cyclic primary amines are elementary building blocks to many fine chemicals, pharmaceuticals, and polymers. Here, a powerful one-pot Raney Ni-based catalytic strategy was developed to transform guaiacol into cyclohexylamine using NH3 (7 bar) and H-2 (10 bar) in up to 94 % yield. The methodology was extendable to the conversion of a wider range of guaiacols and syringols into their corresponding cyclohexylamines. Notably, a crude bio-oil originating from the reductive catalytic fractionation of birch lignocellulose was transformed into a product mixture rich in 4-propylcyclohexylamine, constituting an interesting case of catalytic funneling. The isolated yield of the desired 4-propylcyclohexylamine reached as high as 7 wt % (on lignin basis). Preliminary mechanistic studies pointed at the consecutive occurrence of three key catalytic transformations, namely, demethoxylation, hydrogenation, and amination.

Automated summary

Cyclic primary amines are important building blocks in many chemicals and pharmaceuticals. A powerful catalytic strategy was developed to convert guaiacol into cyclohexylamine with high yield. The method can also be applied to other types of guaiacols. It was found that crude bio-oil from birch lignocellulose can be transformed into a product mixture rich in 4-propylcyclohexylamine.