Palladium-catalyzed cross-coupling of organotellurium compounds with hypervalent iodonium salts

Article abstract of DOI:10.1081/SCC-100103992

The palladium-catalyzed cross-coupling of hypervalent iodonium salts with organotellurium dichloride was achieved with PdCl₂ (10 mol %) in the presence of NaOMe (3 equiv) in CH₃CN/MeOH at room temperature.

Full text of DOI:10.1081/SCC-100103992

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PALLADIUM-CATALYZED
CROSS-COUPLING OF
ORGANOTELLURIUM
COMPOUNDS WITH
HYPERVALENT IODONIUM
SALTS
a
a
a
Suk-Ku Kang , Sang-Woo Lee , Moon-Sik Kim
&
a
Ho-Seok Kwon
a
Department of Chemistry and BK-21 School of
Molecular Science , Sungkyunkwan University ,
Natural Science Campus, Suwon, 440-746, Korea
Published online: 09 Nov 2006.
To cite this article: Suk-Ku Kang , Sang-Woo Lee , Moon-Sik Kim & Ho-Seok Kwon
2001) PALLADIUM-CATALYZED CROSS-COUPLING OF ORGANOTELLURIUM COMPOUNDS
(
WITH HYPERVALENT IODONIUM SALTS, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 31:11, 1721-1725,
DOI: 10.1081/SCC-100103992
To link to this article: http://dx.doi.org/10.1081/SCC-100103992
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SYNTHETIC COMMUNICATIONS, 31(11), 1721–1725 (2001)
PALLADIUM-CATALYZED CROSS-
COUPLING OF ORGANOTELLURIUM
COMPOUNDS WITH HYPERVALENT
IODONIUM SALTS
Suk-Ku Kang,* Sang-Woo Lee, Moon-Sik Kim,
and Ho-Seok Kwon
Department of Chemistry and BK-21 School of Molecular
Science, Sungkyunkwan University, Natural Science
Campus, Suwon 440-746, Korea
ABSTRACT
The palladium-catalyzed cross-coupling of hypervalent iodo-
nium salts with organotellurium dichloride was achieved with
PdCl (10 mol %) in the presence of NaOMe (3 equiv) in
2
CH CN/MeOH at room temperature.
3
Organotellurium compounds are becoming increasingly important in
1
organic synthesis. However utilization of organotellurium compounds in
carbon-carbon bond formation is rather limited. In the literature, cross-
coupling of alkyl or aryltellurides with Grignard reagents in the presence
2
,3
of palladium, cobalt, or nickel catalyst is known. The substitution of the
tellurium moiety of vinyl tellurides has been performed with lower and higher
4
order cuprates. It is also known that vinyltellurides can be exchanged with
5
aluminium or zinc species via transmetallation. Recently Uemura et al.
6
*
Corresponding author.
1
721
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1
722
KANG ET AL.
reported the palladium-catalyzed carbonylation and homocoupling of vinyl
tellurides as well as Heck-type coupling of vinyltellurides. In connection
with our programs to utilize hypervalent iodonium salts in palladium-cata-
7
lyzed cross-coupling. We found that diaryl or divinyltellurium dichlorides
can be readily coupled with iodonium salts in the presence of palladium
catalyst. Here we wish to report palladium-catalyzed cross-coupling of iodo-
nium salts with diaryl or divinyltellurium dichlorides (Eqn 1).
(1)
The results of the palladium-catalyzed cross-coupling of hypervalent
iodonium salts with organotellurium dichlorides are summarized in Table 1.
The p-methoxyphenyl(phenyl)iodonium triflate (1a) reacted with diphenyl-
tellurium dichloride (2a) in the presence of PdCl (10 mol %) and NaOMe
2
(3 equiv) in CH CN/MeOH (1:1) at room temperature for 7 h to afford
3
p-methoxybiphenyl (3a) in 88% yield (entry 1). Of the catalyst tested
PdCl , Pd (dba) , and PdCl (PPh ) , Pd(PPh ) , PdCl was the best
2
2
2
3
2
3 2
3 4
choice. As a solvent, CH CN/MeOH (1:1) was the most suitable among
3
the solvent toluene, CH CN, MeOH, CH CN/MeOH (1:1), DMF tested.
3
3
The addition of NaOMe is critical in this coupling. With the iodonium
salt 1b under the same conditions the coupling gave the same coupled
product 3a in 85% yield. For the di(p-methoxyphenyl)tellurium dichloride
(
2b) the reaction with Ph IBF (1c) gave the cross-coupled product 3a in 81%
2 4
yield (entry 2). When the iodonium salt 1a was reacted with p-methoxyphe-
nyl-substituted tellurium dichloride 2b, 4,4-dimethoxybiphenyl (3b) was
obtained in 81% yield (entry 3). Treatment of 2-thienyl(phenyl)iodonium
tetrafluoroborate (1d) and tosylate (1e) with 2b, 2-(p-methoxyphenyl)thio-
phene (3c) which the 2-thienyl group was coupled was obtained as the sole
product in 86% and 83% yields, respectively (entry 4). This method was
extended to the coupling of alkenyl substituted iodonium salt 1f. Reaction
of the alkenyl iodonium tetrafluoroborate 1f with organotellurium dichlor-
ides and 2a and 2b afforded the product 3d and 3e is 72 and 70% yields,
respectively (entries 5 and 6).
Although the mechanism for this palladium-catalyzed coupling of
organotellurium compounds with hypervalent iodonium salts remains to

ORGANOTELLURIUM COMPOUNDS
1723
Table 1. The Palladium-Catalyzed Cross-Coupling of Organotellurium with Hyper-
valent Iodonium Salts
be elucidated, it is presumed that the oxidative addition of Pd(0) and hyper-
valent iodonium salts to form RPdBF which is subjected to transmetalla-
4
tion with Ar Te(OMe) from Ar TeCl and NaOMe followed by reductive
2
2
2
2
elimination to afford the coupled product (Scheme 1).
Scheme 1.

1
724
KANG ET AL.
In conclusion the palladium-catalyzed cross-coupling of hypervalent
iodonium salts with organotellurium dichlorides was achieved in the
presence of PdCl (10 mol %) at room temperature under mild conditions.
2
EXPERIMENTAL
Typical Procedures
Preparation of p-Methoxybiphenyl (3a)
To a stirred solution of Ph TeCl (716 mg, 1.40 mmol), PdCl (25 mg,
2
2
2
0
.14 mmol), and NaOMe (220 mg, 4.20 mmol) in CH CN/MeOH (20 mL)
3
under nitrogen atmosphere was added 4-methoxyphenyl(phenyl)iodonium
tetrafluoroborate (1a) (556 mg, 1.40 mmol) at room temperature. The reac-
tion mixture was stirred at room temperature for 7 h. The reaction mixture
was extracted with diethyl ether (20 mL ꢀ 3). The organic layer was dried
over anhydrous sodium sulfate and evaporated in vacuo. The crude product
was separated by SiO column chromatography (hexanes, R ¼ 0.17) to
2
f
afford the coupled product 3a (219 mg, 85%). TLC, SiO , hexanes,
2
1
R ¼ 0.17. H NMR (500 MHz, CDCl ) d 3.87 (s, 3H), 7.01 (m, 2H), 7.34
f
3
ꢁ1
(
(
m, 1H), 7.45 (m, 2H), 7.58 (m, 4H). IR (KBr) 3055, 1265, 1115 cm . MS
EI): m/e (relative intensity) ¼ 185 (12), 184 (100), 169 (80), 141 (29), 115.
ACKNOWLEDGMENT
Generous financial supportfrom KOSEF-CMDS (Center for Molecular
Design and Synthesis) is gratefully acknowledged.
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Accepted in the Netherlands August 21, 2000