Aerobic Oxidative Cleavage of C(OH)-C Bonds to Produce Aromatic Aldehydes Catalyzed by CuI -1,10-phenanthroline Complex.

Abstract

Effective cleavage and functionalization of C(OH)-C bonds is of great importance for the production of value-added chemicals from renewable biomass resources such as carbohydrates, lignin and their derivatives. The efficiency and selectivity of oxidative cleavage of C(OH)-C bonds are hindered by their inert nature and various side reactions associated with the hydroxyl group. The oxidative conversion of secondary alcohols to produce aldehydes is particularly challenging because the generated aldehydes tend to be over-oxidized to acids or the other side products. Noble-metal based catalysts are necessary to get satisfactory aldehyde yields. Herein, for the first time, the efficient aerobic oxidative conversion of secondary aromatic alcohols into aromatic aldehydes is reported using non-noble metal catalysts and environmentally benign oxygen, without any additional base. It was found that CuI -1,10-phenanthroline (Cu-phen) complex showed outstanding performance for the reactions. The C(OH)-C bonds of a diverse array of aromatic secondary alcohols were effectively cleaved and functionalized, selectively affording aldehydes with excellent yields. Detailed mechanism study revealed a radical mediated pathway for the oxidative reaction. We believe that the findings in this work will lead to many explorations in non-noble metal catalyzed oxidative reactions.