Aerobic oxidation of alcohols to aldehydes and ketones using ruthenium(III)/Et3N catalyst

A simple, efficient method for oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones has been developed. Using RuCl3/Et3N as catalyst, the oxidation of benzyl alcohol with oxygen could be achieved with 332 h−1 turnover frequency in the absence of solvent. The influence of versatile N‐containing additives on the catalytic efficiency has been discussed. The presence of minor water would substantially promote the catalytic efficiency, and its role in catalysis has been investigated in detail. The insensitive Hammett correlations of the substituted benzyl alcohols, the normal substrate isotope effect (kH/kD = 3.5 at 335 K), and the linear relationship between O2 pressure and turnover frequency imply that the reoxidation of the Ru(III) hydride intermediate to the active species shares the rate‐determining step with the hydride transfer in the catalytic cycle. Copyright © 2011 John Wiley & Sons, Ltd. A simple RuCl3/Et3N system has been explored for alcohol oxidation, and the role of each additive in catalysis has been discussed, which provides a full story of the factors controlling the oxidation in this catalytic system.