ORGANIC
LETTERS
2003
Vol. 5, No. 11
1833-1835
Novel Carbonyl Allylation Mediated by
SnCl2/TiCl3 in Water
,†
Xiang-Hui Tan, Bo Shen, Wei Deng, Hui Zhao, Lei Liu,* and Qing-Xiang Guo*
Department of Chemistry, UniVersity of Science and Technology of China,
Hefei 230026, China
leiliu@chem.columbia.edu; qxguo@ustc.edu.cn
Received February 16, 2003
ABSTRACT
Under the Lewis acid catalysis offered by TiCl3, SnCl2 can efficiently mediate the aqueous Barbier reactions between aldehydes and allyl
chloride or bromide.
Recently, the study of organic reactions occurring in aqueous
media has developed into a very important field.1 In
particular, by virtue of its synthetic potential, mechanistic
intrigue, and operational simplicity, the Barbier coupling
reaction between allyl halide and carbonyl compounds in
aqueous media has attracted considerable attention recently.2
Use of this elegant method allows homoallylic alcohols to
be synthesized in a highly efficient and environmentally
benign way.
some operational problems. For instance, it is often difficult
to stir the reaction mixture when a large amount of metal is
used. Furthermore, metal oxide or hydroxide precipitation
on the surface of metal may slow or stop the reaction.
Water-soluble reductive metal salts such as SnCl2, if
applicable to the aqueous Barbier reaction, may solve the
above operational problems. However, it was reported that
SnCl2 cannot mediate the coupling between allyl halide and
a carbonyl compound in water, unless some Pd(II)14 or
Numerous metals have been reported to be effective in
mediating the aqueous Barbier reaction. Examples include
aluminum,3 magnesium,4 manganese,5 cadmium,6 indium,7
antimony,8 bismuth,9 lead,10 gallium,11 zinc,12 and tin.13
Although good yields can often be obtained in these
reactions, the use of zero-valent metals unavoidably causes
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* Corresponding authors.
† Present address: Department of Chemistry, Columbia University, New
York, NY 10027.
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10.1021/ol034267p CCC: $25.00 © 2003 American Chemical Society
Published on Web 04/29/2003