Palladium-catalyzed selective carbonylation of (E)-1,2-diidoalkenes

Article abstract of DOI:10.1081/SCC-200046514

A mild and selective palladium-catalyzed carbonylation of (E)-1,2-diiodoalkenes protocol for the synthesis of (E)-3-iodoacrylate esters and maleic diesters has been developed. In the presence of PdCI₂, CuCl₂, and CO, (E)-3-iodoacrylate esters and maleic diesters were obtained selectively in moderate yields. Noteworthysis that a clean inversion of configuration takes place in the palladium-catalyzed dicarbonylation of (E)-1,2-diiodoalkenes procedure.

Full text of DOI:10.1081/SCC-200046514

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Palladium‐Catalyzed
Selective Carbonylation of
(E)‐1,2‐Diidoalkenes
Jin‐Heng Li a & Shi Tang a
a Key Laboratory of Chemical Biology & Traditional
Chinese Medicine Research, College of Chemistry
and Chemical Engineering , Hunan Normal
University , Changsha, 410081, China
Published online: 05 Aug 2006.
To cite this article: Jin‐Heng Li & Shi Tang (2005) Palladium‐Catalyzed Selective
Carbonylation of (E)‐1,2‐Diidoalkenes, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 35:1, 105-113, DOI:
10.1081/SCC-200046514
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Synthetic Communicationsw, 35: 105–113, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1081/SCC-200046514
Palladium-Catalyzed Selective
Carbonylation of (E)-1,2-Diidoalkenes
Jin-Heng Li and Shi Tang
Key Laboratory of Chemical Biology & Traditional Chinese Medicine
Research, College of Chemistry and Chemical Engineering,
Hunan Normal University, Changsha, China
Abstract: A mild and selective palladium-catalyzed carbonylation of (E)-1,2-diio-
doalkenes protocol for the synthesis of (E)-3-iodoacrylate esters and maleic diesters
has been developed. In the presence of PdCI2, CuCl2, and CO, (E)-3-iodoacrylate
esters and maleic diesters were obtained selectively in moderate yields. Noteworthysis
that a clean inversion of configuration takes place in the palladium-catalyzed dicarbo-
nylation of (E)-1,2-diiodoalkenes procedure.
Keywords: Carbonylation, (E)-1,2-diiodoalkene, (E)-3-iodoacrylate ester, maleic
diester, palladium
3-Haloacrylate esters and maleic diesters are useful intermediates in organic
synthesis[1–8] and are known to exhibit some biological properties.[9–11] For
these reasons, considerable effort has been directed to the development of
new and selective methods for the synthesis of 3-haloroacrylate esters[12–18]
and maleic diesters.[20–31] Palladium-catalyzed carbonylation of terminal
acetylenes transformation represents an attractive route to the synthesis of
3-haloroacrylate esters and maleic diesters (1k).[18–33] For the synthesis of
maleic diesters, many efficient palladium-catalyzed carbonylation methods
have been developed.[19–31] However, almost all of those methods gave
Received in Japan August 19, 2004
Address correspondence to Jin-Heng Li, Key Laboratory of Chemical Biology &
Traditional Chinese Medicine Research, College of Chemistry and Chemical Engineer-
ing, Hunan Normal University, Changsha 410081, China. E-mail: jhli@hunnu.edu.cn

106
J.-H. Li and S. Tang
a mixture of maleic diesters and fumaric diesters. For 3-haloroacrylate esters,
only one palladium-catalyzed carbonylation method for synthesizing (Z)-3-
chloroacrylate esters has been described.[28] To the best of our knowledge,
no example of the synthesis of 3-iodoacrylate esters via palladium-catalyzed
carbonylation reaction has been reported. Thus, the development of a new
and selective palladium-catalyzed carbonylation approach to form 3-iodoacry-
late esters and maleic diesters would be significant. Here we report a mild and
selective PdCl2-catalyzed carbonylation of l,2-diiodoalkenes method for the
synthesis of (E)-3-iodoacrylate esters and maleic diesters (Eq 1).
Recently, we employed the diiodonation of alkynes efficiently and stereo-
selectively to afford (E)-1,2-diiodoalkenes in quantitative yields with the aid
of either CO2 (l.0 MPa) Or Ce2(SO4)3 (Eq 2),[29,30] which enable us to study
the palladium-catalyzed carbonylation reaction.
Initially, our attempts were to optimize the reaction conditions for the
palladium-catalyzed carbonylation of 1. Carbonylation of (E)-1,2-diiodo-l-
heptene 1a with MeOH and CO was first tested, and the results are summar-
ized in Table 1. The results showed that PdCl2 was the most effective of other
palladium catalysts including PdCl2(MeCN)2, Pd(OAc)2, and Pd(PPh3)4
(entries 1–4). In the presence of PdCl2 (5 mol%), CuCl2 (3 equiv), Et3N
(2 equiv), CO (1 atm), and MeOH (10 mL), 34% yield of the corresponding
monocarbonylation product (E)-2a was obtained together with a trace
amount of a dicarbonylation product 3a. Whereas 26% and 10% yields of
(E)-2a were isolated, respectively, using either PdCl2(MeCN)2 or Pd(OAc)2
as the catalyst. It is noteworthy that trace amounts of the corresponding carbo-
nylation products were observed when Pd(PPh3)4 and Et3N were used as the
catalytic system.
A series of bases including Et3N, NaOAc, and K2CO3 were then
evaluated in the presence of PdC12 (5 mol%), CuCl2 (3 equiv), CO (1 atm),
and MeOH (10 mL). The results indicated that the effect of the bases

Palladium-Catalyzed Selective Carbonylation of (E)-1,2-Diidoalkenes
Table 1. Palladium-catalyzed carbonylation of 1aa
107
Isolated yield (%)
Entry
Pd
Base
Et3N
2a
34
3a
1
PdCl2
Trace
4
2
PdCl2(MeCN)2
Pd(OAc)2
Pd(PPh3)4
PdCl2
Et3N
Et3N
26
10
3
Trace
Trace
26
4b
5
Et3N
Trace
18
60
NaOAc
K2CO3
K2CO3
K2CO3
K2CO3
6
PdCl2
PdCl2
Trace
5
—
7c
8b
9d
46
—
PdCl2
PdCl2
18
Trace
aUnless otherwise indicated, the reaction conditions were as follows: 1a (0.5 mmol),
Pd (5 mol%), CuCl2 (1 atm), and the indicated base (2 equiv) in MeOH (10 mL) at room
temperature for 48 h.
bWithout CuCl2
cCuCl2 (2 equiv).
dO2 (1 atm) instead of CuCl2.
affected both the yield and chemoselectivity, and K2CO3 provided the highest
yield (entries 1, 4, and 5). In the presence of 2 equiv of K2CO3, 60% yield of
(E)-2a was obtained together with a trace amount of 3a. Whereas 34% and
18% yields of (E)-2a were isolated, respectively, using either Et3N or
NaOAc as the base. Futhermore, the major product was the dicarbonylation
product 3a when NaOAc was used as the base. Interestingly, details
analysis of the both crudely isolated product mixture and purified product
by 1H NMR spectroscopy has established that the formation of the essentially
single stereoisomer is the unexpected (Z)-isomer (maleic diester) of 3a rather
than the expect (E)-isomer (fumaric diester) according to (E)-1a, and very
high stereoselectivities of .99% were observed in the palladium-catalyzed
dicarbonylation procedure.
Finally, oxidative reagents were also examined (entries 6–9). The results
demonstrated that the effect of the oxidants had a fundamental effect on the
reaction. Without any oxidative reagent, no desired product was observed
after 48 h in the presence of PdCl2 (5 mol%), K2CO3, (2 equiv), CO (l atm),
and MeOH (10 mL), whereas the present of 3 equiv of CuCl2 resulted in
60% yield of (E)-2a. But the yield of (E)-2a was decreased to 46% with

108
J.-H. Li and S. Tang
decreasing the loadings of CuCl2 to 2 equiv. O2 served as a terminal oxidant
for the conversion of 1a to 2a catalyzed by PdCl2, but was inferior to CuCl2.
Under the optimum reaction conditions, the palladium-catalyzed carbo-
nylation of various 1,2-diiodoalkenes with a number of alcohols including
MeOH and i-PrOH was carried out smoothly, and the results are summarized
in Table 2. The results showed that the chemoselectivity based on the sub-
strates including both 1,2-diiodoalkenes and alcohols. For carbonylation of
(E)-1,2-diiodoalkene 1b and 1c with MeOH and CO, respectively, the corre-
sponding monocarbonylation products (E)-2b and (E)-3b were obtained in
62% and 57% yields, respectively (entries 2 and 4). Surprisingly, substrates
1d and 1e bearing aromatic groups were carbonylated with MeOH and CO
to afford the corresponding dicarbonylation products (Z)-3d and (Z)-3e as
the major products (entries 5 and 7). Treatment of substrate (E)-1e with
MeOH and CO afforded a mixture of 22% yield of (E)-2e and 50% yield of
Table 2. Palladium-catalyzed carbonylation of 1,2-diiodoalkenesa
Yield (%)b
Time
(h)
Entry
1
Substrate
R’OH
2
3
i-PrOH
24
Trace (2a0)
70(3a0)
2
3
4
5
MeOH
i-PrOH
MeOH
MeOH
48
25
24
30
62 (2b)
0 (2b0)
57 (2c)
0 (2d)
trace (3b)
55(3b0)
0 (3c)
68 (3d)
6
7
i-PrOH
10
10
0 (2d0)
22(2e)
51 (3d0)
50(3e)
MeOH
aUnder otherwise indicated, the reaction conditions were as follows: 1a (0.5 mmol),
PdCl2 (5 mol%), CuCl2 (3 equiv), CO (1 atm), and K2CO3 (2 equiv) in R’OH (10 mL) at
room temperature.
bIsolated yield.

Palladium-Catalyzed Selective Carbonylation of (E)-1,2-Diidoalkenes
109
(Z)-3e (entry 7). Interestingly, when the substrates (E)-1a, (E)-1b, and (E)-1d
reacted with CO and i-PrOH, a secondary alcohol, maleic diesters 3a0, 3b0, and
3d0 were obtained exclusively in 70%, 55%, and 51% yields, respectively, in
the presence of PdCl2, (5 mol%), CuCl2 (3 equiv), and K2CO3 (2 equiv)
(entries l, 3, and 6).
A possible mechanism of the palladium-catalyzed carbonylation of 1,2-
diiodoalkenes was proposed as shown in Scheme 1.[10,13–17,19–34] The reaction
of PdCl2, with CO and R’OH occurred readily to afford intermediate 6 with
the aid of base. Intermediate 7 would be formed by the oxidative addition
of intermediate 6 and 1,2-diiodoalkenes 1, followed by alkoxycarbonylation
to afford the product (E)-2 and Pd(0). Finally, the active palladium species
could be regenerated by the oxidization of Pd(0) with CuCl2 to start a new
catalytic cycle. In the meantime, the secondary alkoxycarbonylation would
take place based on the substrates. In the secondary alkoxycarbonylation
procedure, the stereoselectivity toward (Z)-isomer was observed due to
the complex of Pd with carbonyl group (intermediate 9).[34–36] However,
the reason of the chemoselectivity should be further explored.
In summary, we have developed a mild and selective palladium-catalyzed
carbonylation of 1,2-diiodoalkenes protocol for synthesizing both (E)-3-
iodoacrylate ester and maleic diesters. Furthermore, we first observed the
clean inversion of configuration in the palladium-catalyzed dicarbonylation
process. Currently, Further efforts to study the accurate mechanism and
apply the new inversion of configuration in the palladium-catalyzed
protocol, especially the inversion of configuration, in organic synthesis are
underway in our laboratory.
EXPERIMENTAL
1H and 13C NMR spectra were recorded on an INOVA-400 (Varian) spec-
trometers and a Bruker AMX-400 spectrometers with the use of CDCl2 as
the solvent. All reagents were directly used as obtained commercially.
Scheme 1.

110
J.-H. Li and S. Tang
A Typical Procedure for the Palladium-Catalyzed
Carbonylation Reaction
A mixture of 1 (0.5 mmol), PdCl2 (5 mol%), CuCl2 (3 equiv), and K2CO3
(2 equiv) was stirred under atmospheric pressure of CO in R’OH (10 mL) at
room temperature for desired time. After usual workup, the residue was
purified by flash column chromatography to give 2 or 3 (hexane/ethyl
acetate). All products are known.[12–31]
(E)-3-Iodo-oct-2-enoic Acid Methyl Ester (2a)
Colorless oil; 1H NMR (400 MHz) S: 7–76 (s, 1H), 3.76 (s, 3H), 2.48
(t, J ¼ 8.0 Hz, 2H), (1.42–1.33 (m, 6H), 0.90 (t, J ¼ 6.4 Hz, 3H); 13C NMR
(100 MHz) d: 164.0, 143.6, 98.3, 52.3, 33.7, 31.5, 27.4, 22.4, 14.0. MS m/z:
214 (Mþ), 183, 155, 127, 95, 59, 41, 29. MS m/z: 282 (Mþ), 253, 155
( 2 1), 96.
(E)-3-Iodo-undec-2-enoic Acid Methyl Ester (2b)
Colorless oil; 1H NMR (400 MHz) d: 7.76 (s, IH), 3.76 (s, 3H), 2.48
(t, J ¼ 8.0 Hz, 2H), (1.44–1.28 (m, 12H), 0.88 (t, J ¼ 6.4 Hz, 3H); 13C
NMR (100 MHz) d: 164.1, 143.7, 98.2, 52.3, 33.9, 31.8, 29.4, 29.3, 29.2,
27.7, 22.6, 14. 1. MS m/z: 324 (Mþ), 293, 195 ( 2 1), 138.
(E)-2-lodo-but-2-enedioic Acid Dimethyl Ester (2c)
Colorless oil; 1H NMR (400 MHz) S: 6.69 (s, 1H), 3.89 (s, 3H), 3.75
(s, 3H);13C NMR (100 MHz) d: 166.3, 163.5, 133.6, 102.0, 53.5, 52.4. MS
m/z: 270 (Mþ), 239, 211, 208, 143 ( 2 1).
(E)-3-lodo-3-p-methylphenyl)-acrylic Acid Methyl Ester (2e)
White solid, mp 76–798C (uncorrected); 1H NMR (400 MHz) d: 8.18 (s, 1H),
7.24 (d, J ¼ 8.4 Hz, 2H), 7.14 (d, J ¼ 8.0 Hz, 2H), 3.76 (s, 3H), 2.39 (s, 3H);
13C NMR (100 MHz) d: 164.8, 141.3, 129.3, 128.9, 128.6, 127.2, 114.6, 51.6,
29.7. MS m/z: 302 (Mþ), 271, 243, 116.
(Z)-2-Pentyl-but-2-enedioic Acid Dimethyl Ester (3a)
Colorless oil; 1H NMR (400 MHz) d: 5.81 (s, 1H), 3.84 (s, 3H), 3.73 (s, 3H),
2.53 (t, J ¼ 8.0 Hz, 2H), 1.33–1.30 (m, 6H), 0.89 (t, J ¼ 6.4 Hz, 3H); 13C
NMR (100 MHz) d: 169.4, 165.5, 151.2, 118.8, 52.4, 51.8, 34.3, 31.0, 26.5,
22.3, 13.9; MS m/z: 214 (Mþ), 183, 155, 127, 95, 59, 41, 29.

Palladium-Catalyzed Selective Carbonylation of (E)-1,2-Diidoalkenes
111
(Z)-2-Phenyl-but-2-enedioic Acid Dimethyl Ester (3d)
1
Colorless oil; H NMR (400 MHz) d: 7.47 (d, J ¼ 9.6 Hz, 2H), 7.44–7.38
(m, 3H). 6.30 (s, 1H), 3.93 (s, 3H), 3.77 (s, 3H); MS m/z: 220 (Mþ), 205,
189, 161, 102, 76, 65, 59, 51, 39, 29.
(Z)-2-(p-methylphenyl)-but-2-enedioic Acid Dimethyl Ester (3e)
Colorless oil; 1H NMR (400 MHz) d: 7.38 (d, J ¼ 8.0 Hz, 2H), 7.21
(d, J ¼ 8.0 Hz, 2H), 6.30 (s, 1H), 3.95 (s, 3H), 3.78 (s, 3H), 2.38 (s, 3H);
13C NMR (100 MHz) d: 168.6, 165.6, 150.0, 141.2, 130.1, 129.7, 126.6,
115.6, 52.7, 52.0, 21.4. MS m/z: 234 (Mþ), 219, 203, 175, 117, 101, 76,
65, 59, 55, 39, 27.
(Z)-2-Pentyl-but-2-enedioic Acid Diisopropyl Ester (3a0)
Colorless oil; 1H NMR (400 MHz) d: 5.71 (s, I H), 5.18–5.12 (m, 1H); 5.03–
4.80 (m, 1H), 2.30 (t, J ¼ 8.0 Hz, 2H), 1.50–1.44 (m, 2H), 1.30–1.25 (m, 1H),
1.23–1.21 (m, 5H), 0.86 (t, J ¼ 6.4 Hz, 3H); 13C NMR (100 MHz) d: 166.6,
165.3, 148.4, 128.4, 68.9, 68.0, 31.8, 28.9, 27.8, 22.4, 21.8, 21.7, 14.0; MS
m/z: 270 (Mþ), 255, 241, 227, 211, 169, 126, 112, 95, 55, 43, 27.
(Z)-2-Octyl-but-2-enedioic Acid Diisopropyl Ester (3b0)
Colorless oil; 1H NMR (400 MHz) d: 5.69 (s, 1H), 5.15–5.11 (m, 1H); 5.00–
4.96 (m, 1H), 2.28 (t, J ¼ 8.0 Hz, 2H), 1.46–1.42 (m, 2H), 1.28–1.20
(m, 22H), 0.83 (t, J ¼ 6.8 Hz, 3 H); MS m/z: 312 (M þ ), 298, 283, 269,
253, 211, 112, 95, 55, 41.
(Z)-2-Phenyl-but-2-enedioic Acid Diisopropyl Ester (3d0)
1
Colorless oil; H NMR (400 MHz) d: 7.49 (d, J ¼ 7.6 Hz, 2H), 7.41–7.40
(m, 3H), 6.27 (s, 1H), 5.38–5.14 (m, 1H), 5.12–5.07 (m, 1H), 1.38
(d, J ¼ 6.0 Hz, 6H), 1.29 (d, J ¼ 5.6 Hz, 6H); 13C NMR (100 MHz) d:
167.4, 164.3, 148.6, 133.5, 130.3, 128.9, 126.6, 117.6, 69.5, 68.3, 21.8,
21.6. MS m/z: 276 (Mþ), 217, 175, 147, 131, 102, 77, 63, 51, 43, 27.
ACKNOWLEDGMENTS
We thank the National Natural Science Foundation of China (No. 20202002),
Hunan Province Department of Education (No. 02C211), and Hunan Normal
University for financial support.

112
J.-H. Li and S. Tang
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34. Negishi, E. Handbook of Organopalladium Chemistry for Organic Synthesis;
Negishi, E., Ed.; Wiley-Interscience: New York, 2002.
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36. The selectivity can be altered when there are adjacent functional groups that can
coordinate to palladium to form stable five- or six-membered palladiacyclic
intermediates, see: Hegedus, L. S.; Schlosser, M. Organometallics in Synthesis;
Hegedus, L. S., and Schlosser, M., Eds.; John Wiley & Sons: Chichester, 2002;
p. 1123.