Palladium-catalyzed arylation and aryloylation of organostannanes with triarylbismuth(V) derivatives

Article abstract of DOI:10.1081/SCC-100103532

The palladium-catalyzed cross-coupling and carbonylative cross-coupling of pentavalent bismuth(V) derivatives with organostannanes have been achieved in CH₃CN at room temperature.

Full text of DOI:10.1081/SCC-100103532

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PALLADIUM-CATALYZED
ARYLATION AND
ARYLOYLATION OF
ORGANOSTANNANES
WITH TRIARYLBISMUTH(V)
DERIVATIVES
Suk-Ku Kang a , Hyung-Chul Ryu a & Sang-Woo Lee
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 & Sang-Woo Lee (2001)
PALLADIUM-CATALYZED ARYLATION AND ARYLOYLATION OF ORGANOSTANNANES WITH
TRIARYLBISMUTH(V) DERIVATIVES, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 31:7, 1027-1034,
DOI: 10.1081/SCC-100103532
To link to this article: http://dx.doi.org/10.1081/SCC-100103532
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SYNTHETIC COMMUNICATIONS, 31(7), 1027–1034 (2001)
PALLADIUM-CATALYZED ARYLATION
AND ARYLOYLATION OF
ORGANOSTANNANES WITH
TRIARYLBISMUTH(V) DERIVATIVES
Suk-Ku Kang,* Hyung-Chul Ryu,and Sang-Woo Lee
Department of Chemistry, Sungkyunkwan University,
Natural Science Campus, Suwon 440-746, Korea
ABSTRACT
The palladium-catalyzed cross-coupling and carbonyl-
ative cross-coupling of pentavalent bismuth(V) derivatives
with organostannanes have been achieved in CH3CN at room
temperature.
Organobismuth(V) derivatives are known as useful reagents for O-
and N-arylation of alcohols1–4 and amines,5–8 as well as C-arylation9–13
of phenols, enols, and some carbanions. Recently, phenylation of
terminal acetylenes with triphenylbismuth(V) difluoride was reported
by Zefirov et al.14 Rhodium(I)- and palladium-catalyzed carbometho-
xylation of triarylbismuthines(III) was also reported.15–17 However, no
cross-coupling and carbonylative cross-coupling of organostannanes with
organobismuth(V) compounds have been known. Therefore, we report
arylation and aryloylation of organostannanes with organobismuth(V)
derivatives (Scheme 1).
* Corresponding author.
1027
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1028
KANG,RYU,AND LEE
Scheme 1.
The results of the palladium-catalyzed cross-coupling of organo-
bismuth(V) derivatives with organostannanes are summarized in Table 1.
The triphenylbismuth(V) dichloride 1a was reacted with p-methoxyphenyl-
stannane 2a in the presence of PdCl2 (5 mol%) in CH3CN at room tem-
perature for 3 h to afford p-methoxybiphenyl 3a in 79% 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. With Pd(OAc)2 we could get the
coupled product 3a in a similar 75% yield. As suitable solvent, CH3CN was
chosen even if DMF and NMP were also effective. Under the same con-
ditions, treatment of 1a with 2-furyl- and 2-thienyltributylstannanes gave
the coupled products (3b) and (3c) in 89% and 85% yields, respectively
(entries 2 and 3). For the di(p-tolyl)bismuth dichloride (1b), 2-furylstannane
2b was readily coupled to provide 2-p-tolylfuran (3d) in 80% yield (entry 4).
Alternatively, triphenyl bismuth difluoride (1c)18 was reacted with stannanes
2a, 2b, and 2c to afford the cross-coupled products 3a–3c in 81%, 85%, and
80% yields, respectively (entries 5–7). For triphenylbismuth(V) diacetate
(1d)19,20 the coupling with stannanes 2a and 2d furnished 3a and 3e in
76%, and 80% yields (entries 8 and 9). The p-tolylbismuth(V) diacetate
(1e) was also successfully coupled to give 3d and 3f in 83% and 80%
yields (entries 10 and 11). Finally, tri(p-methoxyphenyl)bismuth(V) diace-
tate (1f) was treated with 2-thienyltributylstannane (2c) to afford the
coupled product 3g in 83% yield (entry 12).
We extended this coupling method to carbonylative cross-coupling to
prepare aryl ketones and carbonylative cross-coupling was accomplished
under atmospheric pressure of carbon monoxide under mild conditions in
the presence of the palladium catalyst (Scheme 2).
Scheme 2.

ORGANOSTANNANES
1029
Table 1. Palladium-Catalyzed Cross-Coupling of Organobismuth(V) Derivatives
with Organostannanes
Organobismuth(V)
Compounds
Isolated
Yield (%)
Entry
1
Organostannanes
Product
Ph3BiCl2
1a
79
89
85
2a
3a
2
3
1a
1a
2b
3b
3d
2c
2b
4
5
80
81
1b
3d
3a
Ph3BiF2
1c
2a
6
7
8
1c
1c
2b
2c
2a
3b
3c
3a
85
80
76
Ph3Bi(OAc)2
1d
9
1d
80
83
2d
2b
3e
3d
10
1e
1e
11
12
2c
2c
80
83
3f
1f
3g

1030
KANG,RYU,AND LEE
The results of carbonylative cross-coupling of organobismuth(V) deri-
vatives with organostannanes are summarized in Table 2. The reaction of
triphenylbismuth(V) dichloride (1a) with 2-thienyltributylstannane (2c)
under atmospheric pressure of carbon monoxide in the presence of PdCl2
(5 mol%) in CH3CN at room temperature for 6h afforded 2-thienylaceto-
phenone (4a)21 in 65% yield (entry 1 in Table 2). Under the same conditions
alkynylstannane 2e was readily coupled to give the alkynyl-sbstituted
ketone 4b22 in 63% yield (entry 2). When tri(p-tolyl)bismuth(V) dichloride
(1b) was treated with 2-thienyltributylstannane (2c), the diarylketone
4c was formed as the sole product (entry 3). Under similar conditions
triphenylbismuth(V) difluoride (1c) was smoothly coupled with 2b, 2c, and
alkenylstannane 2f to afford their respective ketones 4d,23 4a, and 4e24 in
moderate yields (entries 4–6). This coupling was also applied to
triarylbismuth(V) diacetates. The bismuth derivative 1d coupled with aryl-
stannane 2g and alkenylstannane 2f to give the products 4f and 4e (entries 7
and 8). For the tri(p-tolyl)bismuth diacetate (1e), the coupling with 2-furyl-
tributylstannane (2b) gave the ketone 4h25 in 79% yield (entry 9). Finally,
tri(2-naphthyl)bismuth diacetate (1g) was treated with stannanes 2g and
2b to afford the arylketones 4i26 and 4j27 in 82% and 81% yields, respect-
ively (entries 10 and 11)
In conclusion, the palladium-catalyzed cross-coupling and carbonyla-
tive cross-coupling of pentavalent triarylbismuth(V) derivatives with
organostannanes were accomplished in CH3CN at room temperature
under mild conditions.
EXPERIMENTAL
Typical Procedures
Preparation of 2-Phenylfuran (3b)
To a mixture of triphenylbismuth dichloride (1a) (511 mg, 1.00 mmol)
and PdCl2 (8.9 mg, 5 mol%) was added 2-(tributylstanyl)furan (2b) (358 mg,
1.00 mmol) under N2 charged at room temperature in CH3CN (20 mL). The
reaction mixture was stirred at room temperature for 3 h, extracted with
ether (20 mLꢀ3), and washed with water (20 mLꢀ3). The organic layer was
dried over anhydrous MgSO4 and evaporated in vacuo. The crude product
was separated by SiO2 column chromatography (hexanes, Rf ¼ 0.52) to
afford coupled product 3b (128 mg, 89%). TLC, SiO2, hexanes, Rf ¼ 0.52.
1H NMR (500 MHz, CDCl3) ꢀ 7.09 (dd, 1H, J ¼ 5.1, 3.5 Hz), 7.27 (m, 2H),
7.32 (dd, 1H, J ¼ 3.5 Hz), 7.38 (m, 2H), 7.62 (m, 2H). IR (KBr) 3070, 1608,

ORGANOSTANNANES
1031
Table 2. Palladium-Catalyzed Carbonylative Cross-Coupling of Organo-
bismuth(V) Derivatives with Organostannanes
Organobismuth(V)
Compounds
Isolated
Yield (%)
Entry
1
Organostannanes
Product
Ph3BiCl2
1a
65
63
2c
4a
4b
2
3
4
1a
2e
2c
70
80
1b
4c
Ph3BiF2
1c
1c
2b
2c
4d
4a
5
6
67
78
1c
2f
4e
7
Ph3Bi(OAc)2
PhSnBu3
PhCOPh
78
1d
1d
2g
2f
4f
8
9
4e
75
79
2g
1b
4h
10
11
2g
2b
82
81
1g
1g
4i
4j

1032
KANG,RYU,AND LEE
1477, 832, 708 cmꢁ1. MS (EI): m/e (relative intensity) ¼ 160 (100), 128 (13),
115 (34), 102 (5), 89 (7).
2-(p-Tolyl)thiophene (3f)
1
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 cmꢁ1. MS (EI): m/e (relative intensity) ¼ 174 (100), 173, 141,
128, 115.
Preparation of 2-Benzoylfuran (4d)
To a mixture of triphenylbismuth difluoride (1c) (478 mg, 1.00 mmol)
and PdCl2 (8.9 mg, 5 mol%) was added 2-(tributylstanyl)furan (2b) (358 mg,
1.00 mmol) under atmospheric CO at room temperature in CH3CN (20 mL).
The reaction mixture was stirred at room temperature for 6h, extracted with
ether (20 mLꢀ3), and washed with water (20 mLꢀ3). The organic layer was
dried over anhydrous MgSO4 and evaporated in vacuo. The crude product
was separated by SiO2 column chromatography (EtOAc/hexanes ¼ 1 : 10,
Rf ¼ 0.46) to afford coupled product 4d (138 mg, 80%): TLC, SiO2,
1
EtOAc/hexanes 1:10, Rf ¼ 0.46. H NMR (500 MHz, CDCl3) ꢀ 7.09 (dd,
1H, J ¼ 5.1, 3.5 Hz), 7.27 (m, 2H), 7.32 (dd, 1H, J ¼ 3.5 Hz), 7.38 (m, 2H),
7.62 (m, 2H). IR (KBr) 3070, 1608, 1477, 832, 708, 900 cmꢁ1. MS (EI): m/e
(relative intensity) ¼ 160 (100), 128 (13), 115 (34), 102 (5), 89 (7).
2-Benzoylnaphthalene (4i)
TLC, SiO2, EtOAc/hexanes 1 : 10, Rf ¼ 0.48. 1H NMR (500 MHz,
CDCl3) ꢀ 7.49 (m, 5H), 7.58 (m, 2H), 7.86(m, 2H), 7.93 (m, 1H), 7.99
(m, 1H), 8.23 (m, 1H). IR (KBr) 3055, 1660, 1265 cmꢁ1. MS (EI): m/e
(relative intensity) ¼ 232 (100), 231, 155, 127, 105, 77.
2-Furyl-2-naphthylmethanone (4j)
TLC, SiO2, EtOAc/hexanes 1 : 10, Rf ¼ 0.46. 1H NMR (500 MHz,
CDCl3) ꢀ 6.57 (m, 1H), 7.06 (m, 1H), 7.54 (m, 3H), 7.73 (m, 1H), 7.80
(m, 1H), 7.91 (m, 1H), 8.02 (m, 1H), 8.22 (m, 1H). IR (KBr) 3055, 1654,

ORGANOSTANNANES
1033
1260 cmꢁ1. MS (EI): m/e (relative intensity) ¼ 223 (11), 222 (73), 221 (48),
194 (13), 165 (72), 155 (30), 127 (100), 95 (32).
ACKNOWLEDGMENTS
Generous financial support from KOSEF-Center for Molecular
Design and Synthesis (CMDS) is gratefully acknowledged.
REFERENCES
1. Finet, J.P. Chem. Rev. 1989, 89, 1487–1501.
2. Aramovitch, R.A.; Barton, D.H.R.; Finet, J.P. Tetrahedron 1988, 44,
3039–3071.
3. Barton, D.H.R.; Finet, J.P.; Khamsi, J.; Pichon, C. Tetrahedron Lett.
1986, 27, 3631–3622.
4. Sinclair, P.J.; Wong, F.; Wyvratt, M.; Staruch, M.J.; Dumont, F.
Bioorg. Med. Chem. Lett. 1955, 5, 1035–1038.
5. Barton, D.H.R.; Finet, J.P.; Pichon, C. J. Chem. Soc., Chem.
Commun. 1986, 65–66.
6. Arnauld, T.; Barton, D.H.R.; Doris, E. Tetrahedron 1997, 53,
4137–4144.
7. Barton, D.H.R.; Finet, J.P.; Khamsi, J. Tetrahedron Lett. 1986, 27,
3615–3618.
8. Chan, D.M.T. Tetrahedron Lett. 1996, 37, 9013–9016.
9. Barton, D.H.R.; Finet, J.P. Pure & Appl. Chem. 1987, 59, 937–946.
10. Barton, D.H.R.; Bhatnager, N.Y.; Blazejealski, J.C.; Charpiot, B.;
Finet, J.P.; Loster, D.J.; Motherwell, W.B.; Barros Papouls, M.T.;
Stanforth, S.P. J. Chem. Soc., Perkin Trans. 1 1985, 2657–2665.
10. Barton, D.H.R.; Blazejewski, J.C.; Charpiot, B.; Finet, J.P.;
Motherwell, W.B.; Barros Popoula, M.T.; Stanforth, S.P. J. Chem.
Soc., Perkin Trans. 1 1985, 2667–2675.
11. Barton, D.H.R.; Finet, J.P.; Giannotti, C.; Halley, F. J. Chem. Soc.,
Perkin Trans. 1 1997, 241–249.
12. Barton, D.H.R.; Bhatnager, N.Y.; Finet, J.P.; Motherwell, W.B.
Tetrahedron 1986, 42, 3111–3122.
13. Barton, D.H.R.; Finet, J.P.; Khamsi, J.; Pichon, C. Tetrahedron Lett.
1986, 27, 3619–3622.
14. Lermontov, S.A.; Rakov, I.M.; Zefirov, N.S.; Stang, P.J. Tetrahedron
Lett. 1996, 37, 4051–4054.

1034
KANG,RYU,AND LEE
15. Cho, C.S.; Yoshimori, Y.; Uemura, S. Bull. Chem. Soc. Jpn. 1995, 68,
905–957.
16. Cho, C.S.; Ohe, T.; Itoh, O.; Uemura, S. J. Chem. Soc., Chem.
Commun. 1992, 453–454.
17. Barton, D.H.R.; Ozbalik, N.; Ramesh, M. Tetrahedron 1988, 44,
5661–5668.
18. The compound Ph3BiF2 was prepared from Ph3BiCl2 and KF accord-
ing to literature procedure. Challenger, F.; Willkinson, J.F. J. Chem.
Soc. 1922, 121, 91–104.
19. Triarylbismuth diacetates were prepared by the literature procedure.
Combes, S.; Finet, J.P. Tetrahedron 1998, 54, 4313–4318.
20. Combes, S.; Finet, J.P. Synth. Commun. 1996, 26, 4567–4575.
21. Kang, S.K.; Lim, K.H.; Ho, P.S.; Yoon, S.K.; Son, H.J. Synth.
Commun. 1998, 28, 1481–1489.
22. Delaude, L.; Masdeu, A.M.; Alper. H. Synthesis 1994, 1149–1151.
23. Benassi, R.; Folli, U.; Iarossi, D.; Schenetti, I.; Taddei, F. J. Chem.
Soc., Perkin. Trans. 1 1987, 1443–1454.
24. Thomas, S.; Stephan, N. J. Organomet. Chem. 1992, 430, C5–C9.
25. Edelmann, D.; Ritter, H.; Stolzenbach, H.; Shubert, W. Ger. Offen. De.
1993, 207, 559.
26. Zadel, G.; Breitmaier, E. Angew Chem. 1992, 104, 1070–1071.
27. Baghos, V.B.; Dos, S.H.; Eskander, E.F. Org. Prep. & Proc. Int. 1993,
25, 305–307.
Accepted May 8, 2000