Palladium-catalyzed cross-coupling of triarylbismuth(V) derivatives with hypervalent iodonium salts

Article abstract of DOI:10.1081/SCC-100103531

The palladium-catalyzed cross-coupling of hypervalent iodonium salts with organobismuth(V) derivatives was accomplished with PdCl₂ (5 mol%) in CH₃CN at room temperature.

Full text of DOI:10.1081/SCC-100103531

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PALLADIUM-CATALYZED
CROSS-COUPLING OF
TRIARYLBISMUTH(V)
DERIVATIVES WITH
HYPERVALENT IODONIUM
SALTS
Suk-Ku Kang a , Hyung-Chul Ryu a & Jae-Won Kim a
a Department of Chemistry, Sungkyunkwan
University, Natural Science Campus, Suwon,
440-746, Korea
Published online: 09 Nov 2006.
To cite this article: Suk-Ku Kang , Hyung-Chul Ryu & Jae-Won Kim (2001)
PALLADIUM-CATALYZED CROSS-COUPLING OF TRIARYLBISMUTH(V) DERIVATIVES WITH
HYPERVALENT IODONIUM SALTS, Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic Chemistry, 31:7, 1021-1026, DOI:
10.1081/SCC-100103531
To link to this article: http://dx.doi.org/10.1081/SCC-100103531
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SYNTHETIC COMMUNICATIONS, 31(7), 1021–1026(2001)
PALLADIUM-CATALYZED CROSS-
COUPLING OF TRIARYLBISMUTH(V)
DERIVATIVES WITH HYPERVALENT
IODONIUM SALTS
Suk-Ku Kang,* Hyung-Chul Ryu,and Jae-Won Kim
Department of Chemistry, Sungkyunkwan University,
Natural Science Campus, Suwon 440-746, Korea
ABSTRACT
The palladium-catalyzed cross-coupling of hypervalent
iodonium salts with organobismuth(V) derivatives was accom-
plished with PdCl2 (5 mol%) in CH3CN at room temperature.
Organobismuth(V) compounds have been known as useful reagents
for O- and N-arylation of alcohols and amines.1–8 Alternatively, pentavalent
bismuth compounds were also utilized in C-arylation of phenols, enols, and
other carbanions.9–14 Recently, phenylation of terminal acetylenes with
diphenylbismuth difluoride was reported by Zefirov et al.15 Although rho-
dium- and palladium-catalyzed carbomethoxylation of triphenylbismuthine
was reported by Uemura et al.16–18 the cross-coupling of organobismuth(V)
compounds has not been known. In connection with our programs to utilize
hypervalent iodonium salts in palladium-catalyzed cross-coupling,19–22 we
report the cross-coupling of triaryl-bismuth(V) derivatives with iodonium
salts (Scheme 1).
* Corresponding author.
1021
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1022
KANG,RYU,AND KIM
The results of palladium-catalyzed cross-coupling of hypervalent iodo-
nium salts with organobismuth(V) derivatives are summarized in Table 1.
The p-methoxyphenyl(phenyl)iodonium triflate (1a) reacted with
triphenyl bismuth(V) dichloride in the presence of PdCl2 (5 mol%) in
Scheme 1.
Table 1. The Palladium-Catalyzed Cross-Coupling of Triarylbismuth(V)
Derivatives with Hypervalent Iodonium Salts
Organobismuth(V)
Compounds
Isolated
Yield (%)
Entry
1
Iodonium Salt
Product
Ph3BiCl2
1a X¼OTf
1b X¼OTs
1c X¼BF4
2a
3a
82
80
85
2
3
1a
Ph3BiF2
2b
3a
3a
89
1a
1b
1c
Ph3Bi(OAc)2
2c
87
77
83
4
74
1d
2d
2d
3b
5
6
70
72
1e
1d
3c
3b
2e
2e
2c
7
8
1e
1e
3c
3d
69
75

TRIARYLBISMUTH(V) DERIVATIVES
1023
the CH3CN at room temperature to afford p-methoxybiphenyl (3a) in 82%
yield (entry 1 in Table 1). Of the catalysts tested [PdCl2, Pd(OAc)2,
Pd(PPh3)4, and PdCl2(dppf)], PdCl2 was the best choice. As a suitable sol-
vent, CH3CN was chosen even though DMF and DME were also effective.
Alternatively, the use of 1b and 1c, which has different counter ions, in
this cross-coupling gave the same coupled product 3a in 80% and 85%
yields, respectively. For the triphenylbismuth(V) difluoride (2b), the
iodonium triflate salt 1a was readily coupled to give 3a in 89% yield
(entry 2). Likewise the triphenylbismuth(V) diacetates (2c) can be utilized
to couple with p-methoxyphenyl(phenyl)iodonium salts 1a–1c to furnish
p-methoxybiphenyl (3a) (entry 3). Treatment of 2-thienyl(phenyl)iodonium
tetrafluoroborate (1d) with tri(p-tolyl)bismuth dichloride (2d) in the pres-
ence of PdCl2 catalyst afforded 2-(p-tolyl)thiophene (3b) as the sole product
in 74% yield (entry 4). This method was also applied to alkenyliodonium
salt. When the compound 2d was coupled with (E)-ꢀ-styryl(phenyl)iodo-
nium tetrafluoroborate (1e), the alkenyl-substituted compound 3c was
obtained as the sole product in 70% yield (entry 5). Alternatively,
tri(p-tolyl)bismuth(V) diacetates (2e) was readily coupled with the iodonium
salt 1d to provide 3b in 72% yield (entry 6). The triarylbismuth diacetate 2e
was reacted with 1e to give the coupled product 3c in 69% yield (entry 7).
Finally, the compound 2c was coupled with (E)-ꢀ-styryl(phenyl)-iodonium
tetrafluoroborate (1e), the alkenyl-substituted compound 3d was obtained
as the sole product in 75% yield (entry 8).
Although the mechanism for this palladium-catalyzed coupling of
organobismuth(V) compounds with hypervalent iodonium salts remains to
be elucidated, it is presumed that the oxidative addition of Pd(0) to hyper-
valent iodonium salts forms RPdX, which is subjected to transmetallation of
Ar3BiX2, followed by reductive elimination to afford the coupled product
(Scheme 2).
Scheme 2.
In conclusion, the cross-coupling of hypervalent iodonium salts
with organobismuth(V) derivatives was achieved in the presence of PdCl2
(5 mol%) at room temperature.

1024
KANG,RYU,AND KIM
EXPERIMENTAL
Typical Procedure: Preparation of p-Methoxybiphenyl (3a)
To a mixture of 4-methoxyphenyl(phenyl)iodonium tetrafluoroborate
(1c) (556mg, 1.40 mmol) and PdCl 2 (13 mg, 0.07 mmol) was added triphenyl-
bismuth dichloride (2a) (716mg, 1.40 mmol) in CH 3CN (20 mL) at room
temperature. The reaction mixture was stirred for 3 h at room temperature.
The reaction mixture was extracted with ether (20 mL Â3) and the organic
layer was dried over anhydrous MgSO4 and evaporated in vacuo. The crude
product was separated by SiO2 column chromatography (hexanes,
Rf ¼ 0.17) to give product (3a) (219 mg, 85%). TLC, SiO2, hexanes,
1
Rf ¼ 0.17. H NMR (500 MHz, CDCl3) ꢁ 3.87 (s, 3H), 7.01 (m, 2H), 7.34
(m, 1H), 7.45 (m, 2H), 7.58 (m, 4H). IR (KBr) 3055, 1265, 1115 cmÀ1. MS
(EI): m/e (relative intensity) ¼ 185 (Mþ), 184 (base peak), 169 (43), 141 (44).
1
2-(p-Tolyl)thiophene (3b): TLC, SiO2, hexanes, Rf ¼ 0.52, H NMR
(500 MHZ, CDCl3) ꢁ 2.37 (s, 3H), 7.06(m, 1H), 7.18 (m, 2H), 7.25 (m, 2H),
7.50 (m, 2H). IR (KBr) 3044, 1602, 900 cmÀ1. MS (EI): m/e (relative
intensity) ¼ 174 (Mþ, base peak), 173, 141, 128, 115.
(E)-ꢀ-(2-p-Tolyl)styrene (3c): TLC, SiO2, hexanes, Rf ¼ 0.43. 1H NMR
(500 MHz, CDCl3) ꢁ 2.37 (s, 3H), 6.94 (d, 2H), 7.17 (m, 3H), 7.29 (m, 3H),
7.42 (m, 3H). IR (KBr) 3055, 2870, 1450, 1265 cmÀ1. MS (EI): m/e (relative
intensity) ¼ 194 (Mþ, base peak), 179 (23), 102 (35).
trans-Stilbene (3d): TLC, SiO2, hexanes, Rf ¼ 0.45. 1H NMR
(500 MHz, CDCl3) ꢁ 7.12 (s, 2H), 7.21 (m, 2H), 7.34 (m, 4H), 7.48 (m, 4
H), IR (KBr) 3019, 1597, 1496, 1072, 962, 909, 765, 693 cmÀ1. MS (EI):
m/e (relative intensity) 180 (88), 179 (100), 178 (72), 165 (45), 89 (32), 76 (24).
ACKNOWLEDGMENTS
Generous financial support by KOSEF-Center for Molecular Design
and Synthesis (CMDS) is gratefully acknowledged.
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Accepted May 8, 2000