Palladium-catalyzed coupling reaction of vinyl epoxides, diol acetonides, and diol carbonates with organobismuth compounds

Article abstract of DOI:10.1081/SCC-100104838

The palladium-catalyzed arylation reaction of vinyl epoxides with organobismuth compounds afforded the aryl-substituted (E)-allylic alcohols via ring opening of epoxides. Alternatively, the palladium-catalyzed reaction of diol acetonides and carbonates wi

Full text of DOI:10.1081/SCC-100104838

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: http://www.tandfonline.com/loi/lsyc20
PALLADIUM-CATALYZED COUPLING REACTION
OF VINYL EPOXIDES, DIOL ACETONIDES, AND
DIOL CARBONATES WITH ORGANOBISMUTH
COMPOUNDS
Suk-Ku Kang , Hyung-Chul Ryu , Young-Taek Hong , Moon-Sung Kim , Sung-
Won Lee & Jung-Hee Jung
To cite this article: Suk-Ku Kang , Hyung-Chul Ryu , Young-Taek Hong , Moon-Sung Kim , Sung-
Won Lee & Jung-Hee Jung (2001) PALLADIUM-CATALYZED COUPLING REACTION OF VINYL
EPOXIDES, DIOL ACETONIDES, AND DIOL CARBONATES WITH ORGANOBISMUTH COMPOUNDS,
Synthetic Communications, 31:15, 2365-2371, DOI: 10.1081/SCC-100104838
To link to this article: http://dx.doi.org/10.1081/SCC-100104838
Published online: 09 Nov 2006.
Submit your article to this journal
Article views: 82
View related articles
Citing articles: 15 View citing articles
Full Terms & Conditions of access and use can be found at
http://www.tandfonline.com/action/journalInformation?journalCode=lsyc20
Download by: [University of Waterloo]
Date: 14 November 2016, At: 00:36

SYNTHETIC COMMUNICATIONS, 31(15), 2365–2371 (2001)
PALLADIUM-CATALYZED COUPLING
REACTION OF VINYL EPOXIDES, DIOL
ACETONIDES, AND DIOL CARBONATES
WITH ORGANOBISMUTH COMPOUNDS
Suk-Ku Kang,* Hyung-Chul Ryu, Young-Taek Hong,
Moon-Sung Kim, Sung-Won Lee, and Jung-Hee Jung
Department of Chemistry, Research Institute for Basic Science,
Sungkyunkwan University, Natural Science Campus,
Suwon 440–746, S. Korea
ABSTRACT
The palladium-catalyzed arylation reaction of vinyl epoxides
with organobismuth compounds afforded the aryl-substituted
(E)-allylic alcohols via ring opening of epoxides. Alternatively,
the palladium-catalyzed reaction of diol acetonides and car-
bonates with bismuth derivatives afforded the aryl-substituted
diol acetonides and carbonates without ring opening.
The use of bismuth salts as Lewis acid catalyst or reagent is reported.1
The application of organobismuth compounds to carbon-carbon bond for-
mation is rather limited. In the literature a self-coupling of Ar3Bi to form
biaryl,2 aryl ketones from heterocyclic bismuth (III) compounds with aryl
halides,3 esters form Ar3Bi and MeOH under CO,4 and the cross-coupling of
*Corresponding author.
2365
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

ORDER
REPRINTS
2366
KANG ET AL.
organobismuth compounds with aryl was triflate was known.5 The Heck
type reaction of Ph3Bi with alkenes afforded the coupled products along
with biphenyl in a low yield.6 In our efforts to utilize organobismuth com-
pounds in organic synthesis,7 we have investigated the palladium-catalyzed
aryl substitution reaction of organobismuth compounds with vinyl epox-
ides, diol acetonides, and diol carbonates, which is shown in Scheme 1.8
The results of the palladium-catalyzed coupling of organobismuth
Scheme 1.
compounds with vinyl epoxides are summarized in Table 1. The vinyl epox-
ide 1a reacted with triphenylbismuthine 2a in the presence of PdCl2
(5 mol%) in DMF/H2O (5:1) at room temperature for 12 h to afford the
phenyl-substituted (E)-allylic alcohol 3a as the sole product in 74% yield
(entry 1 in Table 1). Of the solvents tested DMF/H2O, DMF, toluene,
CH3CN, DMF/H2O (5:1) is the best of choice. Under the same conditions,
tri(p-tolyl)bismuth(III) compound 2b was treated with vinyl epoxide 1a to
give the p-tolyl-substituted (E)-allylic alcohol 3b in 71% yield (entry 2). For
the tri(o-methoxyphenyl)bismuthine 2c, 1a was readily coupled to give the
aryl-substituted (E)-allylic alcohol 3c in 75% yield (entry 3). When tri(thio-
phenoxy)bismuthine 2d9 was reacted with 1a in the presence of PdCl2 the
thiophenyl-substituted (E)-allylic alcohol 3d was provided in 70% yield
(entry 4). This coupling method was extended to the pentavalent
bismuth(V) compounds 2e and 2f. The reaction of the compounds 2e and
2f with 1a furnished the phenyl-substituted alcohol 3a in 69 and 75% yields,
respectively (entries 5 and 6). We also examined the coupling of methyl-
substituted vinyl epoxide 1b as a substrate for the coupling. The reaction of
1b with Ph3Bi (2a) afforded (Z)-and (E)-allylic alcohol 3e in the ratio of 2:5
in 91% combined yield (entry 7). Under the same conditions for 2c in the
presence of PdCl2(dppf) at 70ꢀC the coupling gave the substituted alcohol 3f
in the ratio of 1:2 (Z:E) in 85% yield (entry 8). However when 1b was

ORDER
REPRINTS
ORGANOBISMUTH COMPOUNDS
2367
Table 1. Palladium-Catalyzed Reaction of Vinyl Epoxides with Organobismuth
Compoundsa
aAll the reactions were in run in DMF/H2O (5:1) for 12 h. bThe catalysts were
chosen which gave the best results.
treated with tri(p-tolyl)bismuthine (2b) in the presence of PdCl2(dppf) at
70ꢀC 2-methyl-2-p-tolyl substituted homoallylic alcohol 3g was afforded in
68% yield (entry 9). Instead of PdCl2(dppf), with PdCl2 as a catalyst at
room temperature for 12 h (Z)- and (E)-allylic alcohol 3c (3:1) was obtained

ORDER
REPRINTS
2368
KANG ET AL.
in 90% yield (entry 10). For tri(thiophenoxy)bismuthine 2d the coupling
with 1b afforded thiophenyl-substituted alcohol 3h in 64% yield (entry 11).
The arylation reaction was applied to 1,2-diol acetonides 1c10
and 1,2-diol carbonates 1d9, which the results were summarized in Table
2. The diol acetonide 1c reacted with Ph3Bi (2a) in the presence of
PdCl2 (5 mol%) at room temperature for 12 h to afford the phenyl-
substituted diol acetonide in 38% yield (entry 1). By changing the bismuth
compounds to 2e and 2f the yields became higher and 5a was obtained in 64
and 52% yields, respectively (entries 2 and 3). Under the same mild con-
ditions phenyl substitution reaction was carried out without opening of the
diol cyclic carbonate 1d to afford the phenyl-substituted carbonate 5b in
moderate yields (entries 4–6).8
In summary the palladium-catalyzed arylation reaction of vinyl epox-
ides with organobismuth compounds afforded (E)-allylic alcohols via ring
opening of epoxides. Alternatively, the palladium-catalyzed reaction of
1,2-diol acetonides and carbonates with bismuth derivatives afforded the
aryl-substituted diol acetonides and carbonates without ring opening.
Table 2. Palladium-Catalyzed Coupling Reaction of Diol Acetonides and
Carbonatesa
aAll the reactions were run in the presence of PdCl2 (5 mol%) in DMF/H2O (5:1) for
12 h at room temperature.

ORDER
REPRINTS
ORGANOBISMUTH COMPOUNDS
EXPERIMENTAL SECTION
2369
Typical Procedure
Preparation of (E)-4-Phenyl-but-2-en-1-ol (3a)
To a stirred solution of butadiene monoxide (1a) (34.8 mg, 0.50 mmol),
and triphenylbismuth (2a) (220mg, 0.50mmol) in DMF/H 2O (5:1, 5 mL) was
added PdCl2 (4.50mg, 5 mol%) and stirred at room temperature for 12 h. The
reaction mixture was extracted with diethyl ether (20mL ꢁ 3) and washed
with water. The organic layer was dried over anhydrous MgSO4 and evapo-
rated in vacuo. The crude product was separated by SiO2 column chromato-
graphy (EtOAc/Hexanes 1:1, Rf ¼ 0.36) to afford 4-phenylbut-2-en-1-ol (3a)
(54.4 mg, 74%): TLC, SiO2, EtOAc/hexanes 1:1, Rf ¼ 0.36. 1H NMR
(500 MHz, DMSO) d 3.40(m, 2H), 3.90(m, 2H), 4.64 (t, 1H, J ¼ 5.5 Hz)
5.57 (m, 1H), 5.72 (m, 1H), 7.18 (m, 2H), 7.30(m, 3H). MS (EI): m/e (relative
intensity) ¼ 149 (4), 148 (54), 130 (53), 129 (63), 117 (100), 92 (64), 91 (91),
57 (43).
4-p-Tolyl-but-2-en-1-ol (3b): TLC, SiO2, EtOAc/hexanes 1:1,
1
Rf ¼ 0.34. H NMR (500 MHz, DMSO) d 2.34 (s, 3H), 3.26 (m, 2H), 3.90
(m, 2H), 4.62 (t, 1H, J ¼ 5.5 Hz), 5.57 (m, 1H), 5.71 (m, 1H), 7.07 (m, 4H).
MS (EI): m/e (relative intensity) ¼ 163 (4), 162 (42), 144 (15), 131 (100), 129
(60), 105 (41), 91 (26).
4-(2-Methoxyphenyl)-but-2-en-1-ol (3c): TLC, SiO2, EtOAc/hexanes
1
1:1, Rf ¼ 0.25. H NMR (500 MHz, DMSO) d 3.29 (m, 2H), 3.79 (s, 3H),
3.90(m, 2H), 4.62 (t, 1H, J ¼ 5.5 Hz), 5.55 (m, 1H), 5.73 (m, 1H), 6.88 (m,
1H), 6.97 (m, 1H), 7.18 (m, 1H), 7.21 (m, 1H).
4-Phenylsulfanyl-but-2-en-1-ol (3d): TLC, SiO2, EtOAc/hexanes 1:1,
1
Rf ¼ 0.32. H NMR (500 MHz, DMSO) d 3.56 (m, 2H), 3.84 (m, 1H),
5.00ꢂ5.12 (m, 3H), 5.77 (m, 1H), 7.21 (m, 1H), 7.30(m, 2H), 7.36 (m,
2H). MS (EI): m/e (relative intensity) ¼ 179 (23), 149 (79), 134 (16), 116
(37), 110 (100), 70 (25), 69 (13).
(Z)-2-Methyl-4-phenyl-but-2-en-1-ol (3e): TLC, SiO2, EtOAc/hexanes
1
1:1, Rf ¼ 0.34. H NMR (500 MHz, DMSO) d 1.74 (s, 3H), 3.38 (m, 2H),
4.04 (m, 2H), 4.68 (m, 1H), 5.33 (m, 1H), 7.27 (m, 5H).
(Z)-4-(2-Methoxyphenyl)-2-methyl-but-2-en-1-ol (3f): TLC, SiO2,
1
EtOAc/hexanes 1:1, Rf ¼ 0.24. H NMR (500 MHz, DMSO) d 1.70(s, 3H),
3.26 (t, 2H, J ¼ 8.0Hz), 3.72 (s, 3H), 4.00(d, 2H, J ¼ 6.0Hz), 4.57 (t, 1H,
J ¼ 6.0Hz), 5.26 (t, 1H, J ¼ 8.0Hz), 7.07 (m, 2H), 7.16 (m, 2H).
2-Methyl-2-p-tolyl-but-3-en-l-ol (3g): TLC, SiO2, EtOAc/hexanes 1:1,
Rf ¼ 0.30. 1H NMR (500 MHz, DMSO) d 1.35 (s, 3H), 2.25 (s, 3H), 3.53 (m,
2H), 4.66 ((t, 1H, J ¼ 5.5 Hz), 5.00 (dd, 1H, J ¼ 17.5, 1.5 Hz), 5.06 (dd, 1H,
J ¼ 8.2, 1.5 Hz), 6.05 (dd, 1H, J ¼ 17.5, 8.2 Hz), 7.08 (q, 2H, J ¼ 2.0Hz), 7.20

ORDER
REPRINTS
2370
KANG ET AL.
(q, 2H, J ¼ 2.0Hz). MS (EI): m/e (relative intensity) ¼ 178, 177, 145 (100),
130(22), 128 (13), 150 (Z)-2-Methyl-4-phenylsulfanyl-but-2-en-1-ol ( 3h):
1
TLC, SiO2, EtOAc/hexanes 1:1, Rf ¼ 0.29. H NMR (500 MHz, DMSO)
d 1.68 (s, 3H), 3.26 (s, 2H), 3.77 (d, 2H, J ¼ 7.5 Hz), 4.66 (t, 1H, J ¼ 5.5 Hz),
5.36 (t, 1H, J ¼ 5.5 Hz), 7.17 (m, 5H).
Preparation of (2S, 3S, 4E)-1-O-Benzylxoy-5-(40-phenyl)-4-penten-
2,3-diol acetonide (5a)
To a stirred solution of (2S, 3S)-4-O-benzyloxy-2,3-isopropylidene-
dioxy-4-pentene (1c) (28.0mg, 0.11 mmol) and triphenylbismuth carbonate
(2e) (56.0mg, 0.11 mmol) in DMF/H O (5:1, 5 mL) was added PdCl2
2
(1.0mg, 5 mol%) and stirred at room temperature for 12 h. The reaction
mixture was extracted with diethyl ether (20mL ꢁ 3) and washed with
water. The organic layer was dried over anhydrous MgSO4 and evaporated
in vacuo. The crude product was separated by SiO2 column chromato-
graphy (EtOAc/Hexanes 1:15, Rf ¼ 0.34) to afford (2S, 3S, 4E)-1-
O-benzylxoy-5-(40-phenyl)-4-penten-2,3-diol acetonide (5a) (23.4 mg, 64%):
1
TLC, SiO2, EtOAc/hexanes 1:15, Rf ¼ 0.34. H NMR (500 MHz, CDCl3)
d 1.35 (m, 6H), 3.59 (m, 2H), 3.95 (m, 1H), 4.36 (m, 1H), 4.50(m, 2H),
6.29 (dd, 1H, J ¼ 15.5, 7.3 Hz), 6.63 (d, 1H, J ¼ 15.5 Hz), 7.15 (m, 1H),
7.28 (m, 7H), 7.45 (m, 2H). MS (EI): m/e (relative intensity) ¼ 91 (100),
104 (43), 115 (44), 131 (41), 145 (32), 159 (15), 174 (11), 233 (6), 266 (7),
324 (3).
(2S, 3S, 4E)-1-O-Benzyloxy-5-(40-phenyl)-4-penten-2,3-diol cyclic
carbonate (5b): TLC, SiO2, EtOAc/hexanes 1:4, Rf ¼ 0.25. 1H NMR
(500 MHz, DMSO) d 3.67 (dd, 1H, J ¼ 12.0, 4.0 Hz), 3.80 (dd, 1H,
J ¼ 12.0, 4.0 Hz), 4.53 (m, 1H), 4.64 (d, 2H, J ¼ 6.4 Hz), 5.17 (dd, 1H,
J ¼ 7.3, 7.3 Hz), 6.17 (dd, 1H, J ¼ 15.8, 7.8 Hz), 6.71 (d, 1H, J ¼ 15.8 Hz),
7.36 (m, 10H), IR (neat) 3050, 3025, 1805 cmꢃ1. MS (EI): m/e (relative
intensity) ¼ 219, 131, 115, 91 (100).
ACKNOWLEDGMENT
Generous financial support from Korea Research Foundation Grant
(KRF-2000-015-DP0262) and KOSEF-CMDS (Center for Molecular
Design and Synthesis) is gratefully acknowledged. H-C. Ryu, Y-T. Hong,
and S-W Lee thank the financial support from Brain Korea 21.

ORDER
REPRINTS
ORGANOBISMUTH COMPOUNDS
REFERENCES
2371
1. Review: Suzuki, H.; Ikegami, T.; Matano, Y. Synthesis 1997, 249–267.
2. Barton, D.H.R.; Ozbalik, N.; Ramesh, M. Tetrahedron 1988, 44,
5661–5668.
3. Suzuki, H.; Murafuji, T.; Azuma, N. J. Chem. Soc., Perkin Trans. I
1992, 1593–1600.
4. Cho, C.S.; Yoshinori, Y.; Uemura, S. Bull. Chem. Soc. Jpn. 1995, 68,
950–957.
5. Rao, M.L.N.; Shimada, S.; Tanaka, M. Org. Lett. 1999, 1, 1271–1273.
6. (a) Kawamura, T.; Kikukawa, K.; Takagi, M.; Matsuda, T. Bull.
Chem. Soc. Jpn. 1977, 50, 2021–2024. (b) Asano, R.; Moritani, I.;
Fujiwara, Y.; Teranishi, S. Bull. Chem. Soc. Jpn. 1973, 46, 2910–2911.
7. (a) Kang, S.-K.; Ryu, H.-C.; Kim, J.-W. Synth. Commun. 2001, in
press. (b) Kang, S.-K.; Ryu, H.-C.; Lee, S.-W. Synth. Commun.
2001, in press.
8. We have reported palladium-catalyzed coupling of diol cyclic
carbonates with ring opening with iodobenzene. See, Kang, S.-K.;
Jung, K.-Y.; Park, C.-H.; Jang, S.-B. Tetrahedron Lett. 1995, 36,
8047–8050.
9. The compound 2d was readily prepared by the reaction of
triphenylbismuth(III) with thiophenol in m-xylene at reflux for 15 h
and recrystallized from EtOH or MeOH.
10. Kang, S.-K.; Lee, D.-H.; Sim, H.-S.; Lim, J.-S. Tetrahedron Lett. 1993,
34, 91-94.
Received in the Netherlands November 1, 2000

Request Permission or Order Reprints Instantly!
Interested in copying and sharing this article? In most cases, U.S. Copyright
Law requires that you get permission from the article’s rightsholder before
using copyrighted content.
All information and materials found in this article, including but not limited
to text, trademarks, patents, logos, graphics and images (the "Materials"), are
the copyrighted works and other forms of intellectual property of Marcel
Dekker, Inc., or its licensors. All rights not expressly granted are reserved.
Get permission to lawfully reproduce and distribute the Materials or order
reprints quickly and painlessly. Simply click on the "Request
Permission/Reprints Here" link below and follow the instructions. Visit the
U.S. Copyright Office for information on Fair Use limitations of U.S.
copyright law. Please refer to The Association of American Publishers’
(AAP) website for guidelines on Fair Use in the Classroom.
The Materials are for your personal use only and cannot be reformatted,
reposted, resold or distributed by electronic means or otherwise without
permission from Marcel Dekker, Inc. Marcel Dekker, Inc. grants you the
limited right to display the Materials only on your personal computer or
personal wireless device, and to copy and download single copies of such
Materials provided that any copyright, trademark or other notice appearing
on such Materials is also retained by, displayed, copied or downloaded as
part of the Materials and is not removed or obscured, and provided you do
not edit, modify, alter or enhance the Materials. Please refer to our Website
User Agreement for more details.
Order now!
Reprints of this article can also be ordered at
http://www.dekker.com/servlet/product/DOI/101081SCC100104838