FeCl3 · 6H2O Catalyzed Disproportionation of Allylic Alcohols and
Selective Allylic Reduction of Allylic Alcohols and Their Derivatives
with Benzyl Alcohol
Jialiang Wang,† Wen Huang,† Zhengxing Zhang,† Xu Xiang,† Ruiting Liu,† and
Xigeng Zhou*,†,‡
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and InnoVatiVe Materials,
Fudan UniVersity, Shanghai 200433, People’s Republic of China, and State Key Laboratory of
Organometallic Chemistry, Shanghai 200032, People’s Republic of China
ReceiVed January 14, 2009
Iron chloride has been found to be an efficient catalyst for the disproportionation of allylic alcohols,
which provides a convenient method for selective transformation of allylic alcohols to alkenes and R,ꢀ-
unsaturated ketones. Furthermore, this catalytic system is also effective for highly selective allylic reduction
of allylic alcohols, allylic ethers, and allylic acetates with benzyl alcohol under neutral and convenient
reaction conditions.
Introduction
efficient and selective catalysts for this highly valuable but
challenging transformation.4 Although several catalytic systems
have been reported for effecting this reaction, they have some
shortcomings such as harsh reaction conditions and the lack of
generality.4d-h Consequently, further improvements in this area
are desirable. In particular, on the industrial scale, the application
of environmentally benign and cheap catalysts is essential.
Recently, much attention has been directed toward Lewis acid
catalyzed substitution of the hydroxyl groups of allylic alcohols
using nucleophilic reagents as a powerful method for the
formation of various carbon-carbon and carbon-heteroatom
bonds.5 However, in no case the disproportionation products
are observed. Our continuous interest in Lewis acid catalyzed
nucleophilic substitution reactions of allylic and propargylic
alcohols prompted us to explore this possibility.6 Herein, we
Reduction and oxidation of alcohols are useful and important
in organic synthesis.1 Traditionally, such transformations employ
stoichiometric quantities of reductants (e.g., Bu3SnH) or oxidants
such as potassium dichromate, and most of them involve a toxic
or expensive catalyst.2 Considerable efforts have been made to
devise more acceptable reductants and oxidants such as silanes
and O2, as well as nontoxic and low-cost catalysts.3 In that
scenario, the disproportionation of alcohols represents an
efficient, atom-economical, and versatile transformation due to
the simultaneous formation of easily separable hydrocarbon and
aldehyde/ketone molecules and thus should be of great synthetic
potential. There has been a growing effort in the past to develop
† Fudan University.
‡ State Key Laboratory of Organometallic Chemistry.
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10.1021/jo900070q CCC: $40.75
Published on Web 04/06/2009
2009 American Chemical Society
J. Org. Chem. 2009, 74, 3299–3304 3299