Formylation of aryl halides catalyzed by a silica-supported phosphine palladium complex

Article abstract of DOI:10.1081/SCC-120002705

The formylation of aryl bromides or iodides with sodium formate at atmospheric pressure of carbon monoxide readily proceeded in the presence of a silica-supported phosphine palladium complex in DMF to give the corresponding aldehydes in moderate to good yields.

Full text of DOI:10.1081/SCC-120002705

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FORMYLATION OF ARYL HALIDES CATALYZED BY A
SILICA-SUPPORTED PHOSPHINE PALLADIUM COMPLEX
Ming-Zhong Cai a , Hong Zhao b , Jun Zhou a & Cai-Sheng Song a
a Department of Chemistry, Jiangxi Normal University, Nanchang, P.R. China
b Department of Chemistry, Shangrao Teachers’ College, Shangrao, P.R. China
Version of record first published: 16 Aug 2006.
To cite this article: Ming-Zhong Cai, Hong Zhao, Jun Zhou & Cai-Sheng Song (2002): FORMYLATION OF ARYL HALIDES
CATALYZED BY A SILICA-SUPPORTED PHOSPHINE PALLADIUM COMPLEX, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 32:6, 923-926
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SYNTHETIC COMMUNICATIONS, 32(6), 923–926 (2002)
FORMYLATION OF ARYL HALIDES
CATALYZED BY A SILICA-SUPPORTED
PHOSPHINE PALLADIUM COMPLEX
Ming-Zhong Cai,1, Hong Zhao,2
*
Jun Zhou,1 and Cai-Sheng Song1
1Department of Chemistry, Jiangxi Normal
University, Nanchang, P.R. China
2Department of Chemistry, Shangrao Teachers’
College, Shangrao, P.R. China
ABSTRACT
The formylation of aryl bromides or iodides with sodium
formate at atmospheric pressure of carbon monoxide readily
proceeded in the presence of a silica-supported phosphine
palladium complex in DMF to give the corresponding alde-
hydes in moderate to good yields.
The carbonylation of aryl halides in the presence of palladium cata-
lysts is a very versatile reaction and a convenient method for the synthesis
of various aromatic compounds viz., acids, esters, amides, aldehydes and
ketones.1–6 However, in most cases, homogeneous catalysts such as
Pd(OAc)2, Pd(PPh3)2Cl2 are used and it is difficult to recover them from
products. The practical application of the homogeneous catalysts is limited
*Correspondng author.
923
Copyright & 2002 by Marcel Dekker, Inc.
www.dekker.com

924
CAI ET AL.
by their cost. Polymer-supported metal complexes are currently attracting
great interest because they have the advantages of both homogeneous
and heterogeneous catalyzed processes, the ease of separation of catalyst
from the desired reaction products and the ease of recovery of the catalyst
are most important. Reddy et al.7 reported polymer-anchored phosphine
palladium with a P/Pd of 0.895 catalyzed ethoxycarbonylation of organic
halides in ethanol. Recently we investigated the amidation of aryl halides
catalyzed by a silica-supported bidentate phosphine palladium complex and
the butoxycarbonylation of aryl halides catalyzed by a silica-supported
sulfur palladium complex.8–9 To our knowledge, no formylation of aryl
halides catalyzed by a polymeric palladium catalyst has been reported.
Here we wish to report the formylation of aryl halides with carbon
monoxide and sodium formate in the presence of a silica-supported poly-
g-( p-diphenylphosphinophenyl) propylsiloxane palladium complex (‘‘Si’’-
P-Pd) in DMF.
The formylation was carried out by stirring a suspension of iodo-
benzene, powdered sodium formate and 2 mol% ‘‘Si’’-P-Pd in DMF at
90ꢀC for 8 h at atmospheric pressure of CO, which was bubbled through
the mixture by means of a glass inlet tube in order to prevent the formed
CO2 covering the reaction mixture. This formylation afforded benzaldehyde
in an 78% isolated yield. The catalytic activity of ‘‘Si’’-P-Pd is comparable
to that of the analogous catalyst Pd(PPh3)2Cl2 and the polymeric catalyst
can be separated from products by filtration. The activity of recovered
catalyst was tested for the formylation of iodobenzene for two recycles
and it was found that the yield of benzaldehyde decreased by 3 and 6%,
respectively.
This method was applicable to the formylation of a wide variety of
aryl iodides and bromides at atmospheric pressure of CO, typical results are
summarized in Table 1. As expected, aryl iodides were more reactive than
the bromides, and underwent the formylation at 90ꢀC to afford aldehydes in
good yields. The substituent effects in the aryl iodides appeared to be less
significant than in the aryl bromides. The formylation of aryl bromides were
carried out at 110ꢀC to give aldehydes in moderate yields. The reactivity of

FORMYLATION OF ARYL HALIDES
925
Table 1. Formylation of Aryl Halides with Sodium Formate Under Atmospheric
Pressure of COa
Substrate
(Ar-X)
Temperature
(ꢀC)
Time
(h)
Isolated
Yield (%)
Entry
1
2
3
4
5
6
7
8
9
Iodobenzene
p-Iodotoluene
p-Iodochlorobenzene
p-Iodoanisole
Methyl p-iodobenzoate
Bromobenzene
p-Bromochlorobenzene
p-Bromotoluene
90
90
90
90
8
10
8
12
8
10
10
12
12
15
10
78
75
80
77
81
56
65
51
53
45
60
90
110
110
110
110
110
110
m-Bromotoluene
p-Bromoanisole
Methyl p-bromobenzoate
10
11
aCarried out with 5 mmol of aryl halides, 7.5 mmol of powdered HCOONa, and
0.1 mmol of ‘‘Si’’-P-Pd in DMF (7 ml). The products in Table 1 were identified by
1
IR and H NMR.
bromobenzenes having electron-withdrawing substituents was higher than
that of bromobenzenes having electron-donating substituents. The aryl
chlorides were inactive under these conditions. Therefore, p-iodochloro-
benzene was formylated selectively to p-chlorobenzaldehyde in a good
yield and no terephthalaldehyde was detected.
In conclusion, the silica-supported poly-g-( p-diphenylphosphino-
phenyl) propylsiloxane palladium complex is an efficient catalyst for formy-
lation of aryl halides with sodium formate at atmospheric pressure of
carbon monoxide and provides practical advantages such as easy handling,
separation, and reuse.
EXPERIMENTAL
The silica-supported poly-g-( p-diphenylphosphinophenyl) propyl-
siloxane palladium complex was prepared according to literature,10 the
phosphine content of the complex was 2.94 wt% and the palladium content
was 3.11 wt%. IR spectra were obtained using a Shimadzu IR-435. 1H NMR
spectra were obtained using a JEOL FX-90Q (90 MHz) instrument with
Me4Si as an internal standard in CCl4 or CDCl3 as solvent.

926
CAI ET AL.
Typical Procedure: Formylation of Iodobenzene
To a 50 ml round-bottomed flask, fitted with a gas inlet tube, a mag-
netic stirrer bar and a reflux condensor, were placed ‘‘Si’’-P-Pd(340 mg,
0.1 mmol Pd), and HCOONa (510 mg, 7.5 mmol). The atmosphere was
replaced with carbon monoxide. DMF (7 ml) and iodobenzene (1.02 g,
5 mmol) were added by syringe and a slow stream of CO was passed into
the suspension. The mixture was vigorously stirred at 90ꢀC for 8 h. The
reaction mixture was cooled, dissolved in ether (60 ml). The ‘‘Si’’-P-Pd
was separated from the mixture by filtration, washed with distilled water
(2 ꢁ 10 ml), ethanol (2 ꢁ 10 ml) and diethyl ether (2 ꢁ 10 ml) and reused in
the next run. The ethereal solution was washed with 5% NaOH aqueous
solution (10 ml) and water (4 ꢁ 20 ml). The ethereal layer was dried over
anhydrous magnesium sulfate and concentrated under reduced pressure.
The residue was purified by preparative TLC on silica gel (light petroleum :
ethyl acetate ¼ 7 : 1) to afford 0.41 g (78% yield) benzaldehyde.
ACKNOWLEDGMENT
This work was supported by the Natural Science Foundation of
Jiangxi Province in China.
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Received in the Netherlands March 30, 2001