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Aerobic oxidation of alcohols to aldehydes and ketones using ruthenium(III)/Et 3 N catalyst
Author(s) -
Guo Huajun,
Liu WeiDong,
Yin Guochuan
Publication year - 2011
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.1848
Subject(s) - chemistry , catalysis , ruthenium , hydride , alcohol oxidation , solvent , alcohol , benzyl alcohol , catalytic cycle , turnover number , aldehyde , oxygen , substrate (aquarium) , ketone , medicinal chemistry , organic chemistry , hydrogen , oceanography , geology
A simple, efficient method for oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones has been developed. Using RuCl 3 /Et 3 N 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 ( k H / k D = 3.5 at 335 K), and the linear relationship between O 2 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.