Palladium-catalyzed arylation of allylic alcohols with aryl iodides in water

Article abstract of DOI:10.1081/SCC-100107017

Palladium-catalyzed arylation of allylic alcohols with aryl iodides are shown to occur in the presence of sodium bicarbonate and tetra-n-butylammonium chloride in pure water using palladium acetate as catalyst. β-aromatic carbonyl compounds are obtained in good yields.

Full text of DOI:10.1081/SCC-100107017

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PALLADIUM-CATALYZED ARYLATION OF ALLYLIC
ALCOHOLS WITH ARYL IODIDES IN WATER
Hong Zhao a , Ming-Zhong Cai b , Rong-Hua Hu a & Cai-Sheng Song a
a Department of Chemistry, Jiangxi Normal University, Nanchang, P. R. China
b Department of Chemistry, Jiangxi Normal University, Nanchang, P. R. China
Published online: 16 Aug 2006.
To cite this article: Hong Zhao , Ming-Zhong Cai , Rong-Hua Hu & Cai-Sheng Song (2001): PALLADIUM-CATALYZED
ARYLATION OF ALLYLIC ALCOHOLS WITH ARYL IODIDES IN WATER, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 31:23, 3665-3669
To link to this article: http://dx.doi.org/10.1081/SCC-100107017
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SYNTHETIC COMMUNICATIONS, 31(23), 3665–3669 (2001)
PALLADIUM-CATALYZED
ARYLATION OF ALLYLIC
ALCOHOLS WITH ARYL
IODIDES IN WATER
Hong Zhao, Ming-Zhong Cai,*
Rong-Hua Hu, and Cai-Sheng Song
Department of Chemistry, Jiangxi Normal
University, Nanchang, P. R. China
ABSTRACT
Palladium-catalyzed arylation of allylic alcohols with aryl
iodides are shown to occur in the presence of sodium bicar-
bonate and tetra-n-butylammonium chloride in pure water
using palladium acetate as catalyst. b-aromatic carbonyl com-
pounds are obtained in good yields.
The formation of a carbon-carbon bond by palladium-catalyzed coup-
ling of aryl or vinyl halides with olefins, known as the Heck reaction, has
become a powerful tool in organic chemistry.1 In the case of allylic alcohols,
palladium-catalyzed reaction of aryl halides usually affords b-aromatic car-
bonyl compounds.2 Jeffery3 reported that in the presence of sodium bicar-
bonate and tetra-n-butylammonium chloride, a highly selective formation of
* Corresponding author.
3665
Copyright & 2001 by Marcel Dekker, Inc.
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3666
ZHAO ET AL.
b-aromatic carbonyl compounds can be achieved using palladium acetate
as catalyst, the reaction being performed in N,N-dimethylformamide. The
Heck reactions are usually carried out in anhydrous organic solvents.1a
The use of water as a reaction medium for transition metal catalyzed
reactions is very attractive for organic synthesis,4 for both economic and
safety reasons. Bumagin et al5 investigated the carbonylation of aryl iodides,
the coupling reactions of aryl halides with boronic acids and the arylation of
water insoluble olefins in neat water in the presence of palladium salts PdX2.
The reactions proceeded, under mild conditions, with high rates and good
yields. Here we wish to report the palladium-catalyzed arylation of allylic
alcohols with aryl iodides in neat water without any organic co-solvent
(Scheme 1), a highly selective formation of b-aromatic carbonyl compounds
can be achieved.
Scheme 1.
Treatment of 3-buten-2-ol (3 mmol) with iodobenzene (1 mmol) in neat
water (3 ml) at 80ꢀC for 20 h in the presence of a catalytic amount of
Pd(OAc)2 (0.02 mmol), sodium bicarbonate (2.5 mmol) and tetra-n-butylam-
monium chloride (0.1 mmol) afforded 4-phenyl-2-butanone in a 87% yield.
The arylation of 3-buten-2-ol with substituted iodobenzene also proceeded
smoothly in water under the same conditions and a variety of 4-aryl-2-
butanones were obtained in good yields. The results are
summarized in Table 1. 4-Aryl-2-butanones all showed strong IR bands at
1
about 1710 cmꢁ1, and their H NMR spectra were consistent with the pro-
posed structures. The arylation reaction of 3-buten-2-ol with bromobenzene
in water in the presence of a catalytic amount of Pd(OAc)2 and PPh3 was
slow and a mixture of 4-phenyl-2-butanone (32%) and 4-phenyl-3-buten-2-
ol (48%) was formed after 48 h. A similar observation has been made by
Heck2a using triethylamine as the base.
This method was applicable to the arylation of 2-propen-1-ol and
2-methyl-2-propen-1-ol with aryl iodides in neat water and a variety of
3-arylaldehydes were obtained in good yields. These results are also
shown in Table 1. 3-Arylaldehydes all showed strong IR bands at about
1
1720 cmꢁ1, and their H NMR spectra were consistent with the proposed

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ALLYLIC ALCOHOLS
3667
Table 1. Palladium-Catalyzed Arylation of Allylic Alcohols with Aryl Iodides in
Neat Watera
Entry
1
Aryl Iodide
C6 H5I
Allylic Alcohol
t/h
Product (Yield, %)b
—
CH CHCH(OH)CH
—
20 C6H5CH2CH2
C(O)CH3(87)
17 4-ClC6H4CH2CH2
C(O)CH3(84)
24 4-CH3OC6H4CH2
CH2C(O)CH3(86)
22 4-CH3C6H4 CH2CH2
C(O)CH3(80)
20 C6H5CH2CH2
CHO(85)
2
3
3
3
3
—
CH CHCH(OH)CH
—
2
3
4-ClC6H4I
2
—
4-CH3OC6H4I CH CHCH(OH)CH
—
2
—
CH CHCH(OH)CH
—
2
4
4-CH3C6H4I
C6H5I
—
CH CHCH OH
—
5
2
2
—
CH CHCH OH
—
6
4-ClC6H4I
18 4-ClC6H4CH2CH2
CHO(82)
2
2
—
4-CH3OC6H4I CH CHCH OH
—
7
24 4-CH3OC6H4CH2
CH2CHO(84)
2
2
—
CH CHCH OH
—
8
4-CH3C6H4I
C6H5I
23 4-CH3C6H4CH2
CH2CHO(79)
20 C6H5CH2CH(CH3)
CHO(81)
2
2
—
CH C(CH )CH OH
—
9
2
3
2
—
CH C(CH )CH OH
—
10
11
12
4-ClC6H4I
17 4-ClC6H4CH2CH(CH3)
CHO(83)
23 4-CH3OC6H4CH2
CH(CH3)CHO(80)
21 4-CH3C6H4CH2CH(CH3)
CHO(75)
2
3
2
—
4-CH3OC6H4I CH C(CH )CH OH
—
2
3
2
—
CH C(CH )CH OH
—
2 3 2
4-CH3C6H4I
aReactions were carried out at 80ꢀC with 1 mmol of aryl iodide, 3 mmol of allylic
alcohol, 0.02 mmol of Pd(OAc)2, 2.5 mmol of NaHCO3, and 0.1 mmol of Bu4NCl in
3 ml of H2O.
bYields are of isolated, pure products and based on the aryl iodides.
structures. As seen from the Table 1, there is no noticeable difference in
reactivity between iodobenzenes having electron-withdrawing groups and
iodobenzenes having electron-donating groups.
The arylation reaction is highly regioselective with respect to the
addition of the aromatic group, only b-substitution is observed. The
structural isomer selectivity is also very high, only traces of b-aromatic
a,b-unsaturated alcohol compounds are obtained. But in the presence
of sodium carbonate instead of sodium bicarbonate, the arylation
reaction of allylic alcohols with aryl iodides afforded b-aromatic carbonyl

ORDER
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3668
ZHAO ET AL.
compounds as the main products together with a considerable amounts of
b-aromatic a,b-unsaturated alcohol compounds.
In conclusion, the palladium-catalyzed arylation of allylic alcohols
with aryl iodides in neat water described here has not only high regioselec-
tivity and structural isomer selectivity, but offers advantages of being a
simple and practical procedure, carried out under mild reaction conditions
and giving good yields.
EXPERIMENTAL
IR spectra were obtained using a Shimadzu IR-435 grating spectra-
1
photometer. H NMR spectra were recorded on a JEOL FX-90Q(90 MHz)
instrument with TMS as an internal standard in CCl4 or CDCl3 as solvent.
All reagents were used as received without further purification.
Typical Procedure: Synthesis of 4-phenyl-2-butanone
To a 50 ml round-bottomed flask, fitted with a magnetic stirrer bar and
a reflux condensor, were placed Pd(OAc)2 (4 mg, 0.02 mmol), iodobenzene
(0.204 g, 1 mmol), 3-buten-2-ol (0.216 g, 3 mmol), NaHCO3 (0.210 g,
2.5 mmol), Bu4NCl (28 mg, 0.1 mmol), and H2O (3 ml). The mixture was
stirred vigorously at 80ꢀC for 20 h under nitrogen. The reaction mixture
was cooled and dissolved in diethyl ether (50 ml). The ethereal solution
was washed with water (4 ꢂ 30 ml), dried over anhydrous MgSO4, and
then concentrated under reduced pressure. The residue was purified by pre-
parative TLC on silica gel (light petroleum : ethyl acetate ¼ 8 : 1) to afford
0.129 g (87% yield) of 4-phenyl-2-butanone.
ACKNOWLEDGMENT
This work was supported by the Natural Science Foundation of
Jiangxi Province.
REFERENCES
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Org. React. 1982, 27, 345; (c) Davis, G.D. Jr.; Hallberg, A. Chem.

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ALLYLIC ALCOHOLS
3669
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Received in the Netherlands February 5, 2001

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