Aerobic Oxidation of Alcohols Catalyzed by Iron or Vanadium Compounds - Transition Metal Catalysis in Aerobic Alcohol Oxidation - page 155

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CHAPTER 6
Aerobic Oxidation of Alcohols
Catalyzed by Iron or Vanadium
Compounds

MASAYUKI KIRIHARA

Department of Materials and Life Science, Shizuoka Institute of Science
and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka, 437-8555, Japan
Email: [e-mail]

6.1 Oxidations Catalyzed by Iron Compounds

6.1.1 Fe(NO 3 ) 3 -FeBr 3 -Catalyzed Aerobic Oxidation
The first practical aerobic oxidation of an alcohol catalyzed by iron
compounds was reported by Martin and Su´rez in 2002 (Scheme 6.1). 1 Based
on their earlier report of the ecient and selective aerobic oxidation of
sulfides to sulfoxides with a binary system of Fe(NO 3 ) 3 and FeBr 3 , 2 they
successfully attempted the aerobic oxidation of alcohols using the same
catalytic system. Several secondary and benzylic alcohols were eciently
oxidized in the presence of catalytic amounts of the binary Fe( III ) system. It is
interesting that primary alcohols are inert under the reaction conditions.
Therefore, a secondary alcohol, even in the presence of a primary alcohol,
can be selectively oxidized to produce a hydroxy ketone using this method.
Furthermore, the presence of an amino group in the substrate did not
interfere with the oxidation process. Two active species may be at work in the
Fe( III )-catalyzed reaction, either oxidation by NO 2 or oxidation by a bromide-
bromine couple controlled by Fe( III ). 1

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