Palladium-catalyzed intermolecular three-component coupling of organic halides with alkynes and alkenes: Efficient synthesis of oligoene compounds

Article abstract of DOI:10.1002/adsc.200700171

The intermolecular three-component coupling of aryl or vinyl halides, diarylacetylenes, and monosubstituted alkenes effectively proceeds in the presence of palladium acetate, lithium chloride, and sodium bicarbonate as catalyst, promoter, and base, respectively, in aqueous DMF or DMSO to produce the corresponding 1,3-butadiene or 1,3,5-hexatriene derivatives. Use of dienyl bromides allows the coupling to afford 1,3,5,7-octatetraenes. Under the present catalytic conditions, fulvene derivatives are also formed efficiently by the 1:2 coupling of vinyl bromides and diarylacetylenes without adding the alkenes.

Full text of DOI:10.1002/adsc.200700171

FULL PAPERS
DOI: 10.1002/adsc.200700171
Palladium-Catalyzed Intermolecular Three-Component Coupling
of Organic Halides with Alkynes and Alkenes: Efficient Synthesis
of Oligoene Compounds
Kana Shibata,a Tetsuya Satoh,a,* and Masahiro Miuraa,*
a
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
Fax : (+81)-6-6879-7362; e-mail: satoh@chem.eng.osaka-u.ac.jp or miura@chem.eng.osaka-u.ac.jp
Received: April 4, 2007
Supporting information for this article is available on the WWW under http://asc.wiley-vch.de/home/.
Abstract: The intermolecular three-component cou- pling to afford 1,3,5,7-octatetraenes. Under the pres-
pling of aryl or vinyl halides, diarylacetylenes, and ent catalytic conditions, fulvene derivatives are also
monosubstituted alkenes effectively proceeds in the formed efficiently by the 1:2 coupling of vinyl bro-
presence of palladium acetate, lithium chloride, and mides and diarylacetylenes without adding the al-
sodium bicarbonate as catalyst, promoter, and base, kenes.
respectively, in aqueous DMF or DMSO to produce
the corresponding 1,3-butadiene or 1,3,5-hexatriene Keywords: alkynes; C C coupling; Heckreaction;
derivatives. Use of dienyl bromides allows the cou- multicomponent reactions; oligoenes; palladium
À
Introduction
sively,[1,2] the fully intermolecular versions to afford p-
conjugated acyclic compounds have been less ex-
The palladium-catalyzed arylation and vinylation of plored.[3,4] As one of the rare but efficient examples,
internal alkynes by the corresponding halides or their Larockand co-worekrs recently reported the 1:1:1
synthetic equivalents via carbometalation are power- coupling of aryl or vinyl iodides, internal alkynes, and
ful tools for the construction of p-conjugated mole- organoboron reagents involving the Suzuki–Miyaura
cules.[1] Such reactions are often carried out with the coupling in the termination step.[3b–d] We also demon-
addition of various terminators including organome- strated that two molecules of alkynes can be inserted
tallic reagents, alkenes, and terminal alkynes to give between aryl halides and arylboronic acids to produce
rise
(Scheme 1).
to
three-component
coupling
products the corresponding 1:2:1 coupling products, 1,4-diaryl-
1,3-butadienes, when a suitable base such as silver car-
While the reactions via intramolecular cyclization bonate is used.[5]
with alkynylhaloarenes followed by intermolecular
During the course of our study of the catalytic pro-
termination or the reverse with substrates such as al- cesses involving carbometalation of alkynes,[5–7] we
kenylhaloarenes and alkynes have been studied exten- observed that the 1:1:1 coupling of aryl halides, diaryl-
acetylenes, and monosubstituted alkenes can take
place selectively under palladium catalysis by employ-
ing appropriate conditions to give the corresponding
1,3-butadiene derivatives (Scheme 2).[7] This repre-
sents a rare example for the above intermolecular
three-component coupling involving the Mizoroki–
Scheme 1. Palladium-catalyzed three-component coupling of
organic halides, alkynes, and terminators.
Scheme 2. Palladium-catalyzed three-component coupling of
aryl halides, alkynes, and alkenes.
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and alkenes 3a–g. As expected, the reaction using the
substrate combination of an aryl iodide and a diaryl-
acetylene, in which same aryl groups are contained,
with 3a gave the corresponding butyl 4,5,5-triaryl-2,4-
pentadienoate as the predominant product. Thus,
dienes 6a–d were obtained from 1a–d and 2a–d (en-
tries 1–4). The alkenes with an electron-withdrawing
group such as ethyl acrylate (3b), N,N-dimethylacryl-
amide (3c), and acrylonitrile (3d) smoothly reacted
with 1a and 2a to produce the corresponding dienes
6e–g (entries 5–7). Styrene (3e) also underwent the
three-component coupling to afford 1,1,2,4-tetraphen-
Scheme 3. Palladium-catalyzed coupling of vinyl bromides
with alkynes in the presence or absence of alkenes.
[8]
Heckreaction with alkenes in the termination step.
The reaction employing various b-bromostyrenes in yl-1,3-butadiene (6h). In this case, the addition of
place of aryl halides also proceeds to afford 1,3,5-hexa- PPh3 (10 mol%) was found to improve the yield of 6h
triene derivatives (Scheme 3). In the absence of the (entry 9 vs. 8) The use of 4-methyl- and 4-chlorostyr-
alkenes, the bromides couple with two molecules of enes, 3f and 3g, afforded the corresponding dienes 6i
the alkynes to produce fulvene derivatives efficient- and 6j (entries 10 and 11).
ly.[9] The details of the results obtained with respect to
A plausible mechanism for the reaction of aryl hal-
the scope and limitations for these reactions are de- ides 1 with diarylacetylenes 2 and alknens 3 is illus-
scribed herein.
trated in Scheme 4. The formation of an arylpalladi-
um intermediate A via oxidative addition of 1 toward
Pd(0) species generated in situ followed by insertion
of 2 forms a vinylpalladium intermediate B. Then,
successive insertion of 3, b-hydrogen elimination, and
Results and Discussion
First, 4-iodotoluene (1b) was reacted with diphenyl- release of HX to regenerate Pd(0) may occur to allow
acetylene (2a) (1 equiv.) and butyl acrylate (3a) the catalytic production of dienes 4 and 6. The com-
(1 equiv.) under conditions similar to those employed petitive insertions of 2 and 3 into A may be the prin-
for the reaction of 1b with 2a and arylboronic acids.[5] cipal selectivity-determinating steps that lead to diene
In the presence of Pd
A
(1 equiv.) in 1-propanol/H2O (9:1) at 1208C for 20 h, of the reaction of 1b with 2a and 3a in Table 1 imply
butyl
5-(4-methylphenyl)-4,5-diphenyl-2,4-pentadi- that E/Z isomerization takes place in the next inter-
enoate (4) was formed in 16% yield along with a mediate B.[10] The lackof double insertion of 2 sug-
normal Mizoroki–Heck-type product, butyl 3-(4- gests that the reaction of B with 3 is significantly
methylphenyl)-2-propenoate (5), in 25% yield faster than that with 2, while the reasonn is not clear
(Table 1, entry 1). In this case, a trace amount of 1:2 at the present stage.
coupling product, methyl(tetraphenyl)naphthalene,
The synthesis of 1,3,5-hexatrienes by the reaction of
was also detected by GC-MS.[6d] The reaction rate was b-bromostyrenes with alkynes and alkenes was next
found to be enhanced significantly by using DMF/ examined. Treatment of b-bromostyrene (7a)
H2O as solvent (entry 2). Various bases could be used [(E):(Z)=6.5:1] with 2a (4 equivs.) and 3a (1 equiv.)
in place of Ag2CO3 (entries 3–7), and among those ex- in the presence of Pd
(OAc)2 (5 mol%), PPh3 (10
amined relatively weakand less expensive NaHCO mol%), LiCl (0.7 equivs.), and NaHCO3 (2 equivs.) in
3
gave the best result (entry 7). The use of excess 2a DMF/H2O (9:1) at 1208C for 2 h gave the 1:1:1 cou-
(4 equivs.) improved the selectivity for the desired pling product, butyl (2E,4E,6E)-4,5,7-triphenyl-2,4,6-
three-component coupling product 4 (entry 4 vs. 3). heptatrienoate (8a) in 44% yield, along with the Miz-
When the reaction was conducted with the addition oroki–Heck-type coupling product of 7a and 3a, butyl
of LiCl (0.7 equivs.) as promoter at 1308C, 4 was ob- 5-phenyl-2,4-pentadienoate (9) (9%) and the 1:2 cou-
tained in a further improved yield of 72% with a sup- pling-cyclization product of 7a and 3a, 1,2,3,4,6-penta-
pressed amount of 5 (entry 10). The NMR spectra of phenylfulvene (10a) (14%) (Table 3, entry 1). It
4 isolated in entry 10 indicated that it consists of two should be noted that all the double bonds of the hexa-
geometrical isomers [(2E,4E):(2E,4Z)=1.2:1]. Either triene had exclusively (E)-configurations, no other
U
decreasing or increasing the amount of LiCl resulted geometrical isomers being detected by GC-MS and
in a reduction in the yield of 4 (entries 11 and 12). 4- NMR. This contrasts with the fact that the three-com-
Bromotoluene (1b’) could be used in place of 1b with ponent product 4 in Table 1 was a mixture of two geo-
the addition of P
(entry 14).
ACHTREUNG
Table 2 summarizes the results for the reactions of geometrical isomers. In the absence of LiCl, the yield
various aryl iodides 1a–d with diarylacetylenes 2a–d of undesired 9 significantly increased (entry 2). Under
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Palladium-Catalyzed Intermolecular Three-Component Coupling of Organic Halides
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Table 1. Reaction of 4-halotoluene (1b or 1b’) with diphenylacetylene (2a) and butyl acrylate (3a).[a]
[a]
Reaction conditions: [1b or 1b’]:[2a]:[3a]:[Pd(OAc)2]=1:4:1:0.05 (in mmol), in DMF/H2O (9:1, 5 mL) under N2.
GC yield based on the amount of 1 used. Value in parentheses indicates yield after purification.
2a (1 mmol) was used.
In 1-propanol/H2O (9:1, 5 mL).
N
[b]
[c]
[d]
[e]
[f]
In DMSO/H2O (9:1, 5 mL).
(2E,4E):
ACHTREUNG
[g]
With P
ACHTREUNG
such conditions, Cs2CO3 and NEt3 were less effective afford the corresponding 7-aryl-4,5-diphenyl-2,4,6-
than NaHCO3 (entries 3 and 4). When the reaction heptanoates 8b–f. While the triene 8b consisted of the
was conducted in DMSO/H2O, the yield of 8a was en- single isomer having all (E)-configuration (entry 1),
hanced up to 53% (entry 5). In other solvents such as contamination of each (2E,4Z,6E)-isomer was ob-
DMAc/H2O, NMP/H2O, and 1-propanol/H2O, the re- served in the case of 8c–f (entries 2–5). 1-Bromo-4-
action was less efficient (entries 6–8). Eliminating phenyl-1,3-butadiene (7g) also reacted with 2a and 3a
PPh3 and decreasing or increasing the reaction tem- to give butyl (2E,4E,6E,8E)-4,5,9-triphenyl-2,4,6,8-
perature resulted in slightly lower yields of 8a (en- nonatetraenoate (8g) in 42% yield (entry 6).
tries 9–11).
The reactions of 7a with bis(4-methoxyphenyl)- and
A number of hydroxy- and/or methoxy-substituted bis(4-chlorophenyl)acetylenes, (2e) and (2c), in the
cinnamic acids such as coumaric- and sinapinic acids presence of 3a tookplace to afford the corresponding
occur in common agricultural residues and are readily trienes 8h and 8i, respectively (entries 7 and 8). Ethyl
available. Such acids, as well as related other ones, acrylate (3b) and N,N-dimethylacrylamide (3c) also
smoothly underwent decarboxylative bromination reacted with 7a and 2a effectively to afford trienes 8j
under the reported conditions[11] to give the corre- and 8k (entries 9 and 10).
sponding b-bromostyrenes. Using the bromides thus
As expected, the fulvene 10a was formed as the
prepared, the three-component coupling with 2a and single major product, when the reaction of 7a with 2a
3a was examined. As shown in Table 4, a number of was conducted in the absence of any alkenes. The re-
substituted b-bromostyrenes 7b–e and 2-(2-thienyl)- action was found to proceed efficiently without any
ethenyl bromide (7f) underwent the reaction to additives such as LiCl and PPh3. Thus, a series of
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Table 2. Reaction of aryl iodides 1 with diarylacetylenes 2 and alkenes 3.[a]
[a]
Reaction conditions: [1]:[2]:[3]:[Pd
1308C under N2.
GC yield based on the amount of 1 used. Value in parentheses indicates yield after purification.
In each run, a minor amount of Mizoroki–Heck type product (ArCH=CHR) was also formed (3–26%).
With PPh3 (0.1 mmol).
A
G
A
[b]
[c]
[d]
Scheme 4. A plausible mechanism for the reaction of 1 with 2 and 3.
vinyl bromides 7 was treated with 2 (2 equivs.) in the
presence of Pd
(2 mmol) in DMF at 1208C and the corresponding ful- as well as organic glasses[13] has recently been dis-
venes 10a–j were obtained selectively (Table 5). closed. Although some palladium-catalyzed reactions
The application of 1,2,3,4,6-pentaarylfulvenes as the
A
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Table 3. Reaction of b-bromostyrene (7a) with diphenylacetylene (2a) and butyl acrylate (3a).[a]
[a]
Reaction conditions: [7a]:[2a]:[3a]:[Pd
N2 at 1208C.
GLC yield based on the amount of 7a used. Value in parentheses indicates yield after purification.
Without LiCl.
Without PPh3.
At 1008C.
A
G
N
G
[b]
[c]
[d]
[e]
[f]
At 1308C.
of vinyl halides with alkynes to form fulvenes were re- insertion of 2 followed by cyclization to lead to ful-
ported previously, the efficiencies were moderate.[9a–d] vene 10.
Recently, Takahashi and co-workers reported that
It was found that pentadienoate 6a, obtained by the
pentasubstituted fulvenes can be produced effectively three-component coupling of 1a with 2a and 3a, can
by the reaction of vinyl iodides with alkynes using be converted to the corresponding nonatetraenoate
Ag2CO3 as a base.[9e] The present reaction appears to (homologation). Thus, as depicted in Scheme 6, dienyl
be synthetically useful, since readily available vinyl bromide 11 was prepared via hydrolysis and decar-
bromides reacted smoothly even when using the boxylative bromination[11] of 6a. As expected, 11 un-
common, inexpensive base, NaHCO3.
derwent the second three-component coupling with
A plausible mechanism for the reaction of vinyl 2a and 3a to give butyl 4,5,8,9,9-pentaphenyl-2,4,6,8-
bromides 7 with diarylacetylenes 2 in the presence or nonatetraenoate 12, that has exclusively (E)-configu-
absence of alkenes 3 is illustrated in Scheme 5. The ration. As a whole, the 1:2:2 couping of 1a, 2a, and 3a
À
three-component coupling appears to proceed via fun- was achieved forming four C C bonds. On the other
damental steps as in the reaction of aryl halides 1 hand, treatment of 11 with 2a in the absence of 3a ef-
(Scheme 4). Thus, triene 8 may be constructed via oxi- ficiently afforded fulvene 13 by 1:2 coupling.
dative addition, successive alkyne-alkene insertion,
and b-hydrogen elimination steps. The fact that the
(2E,4E,6E)-isomers of 8 were formed predominantly, Conclusion
or even exclusively in some cases, suggests that the di-
enylpalladium intermediate C appears to tend to We have demonstrated that the three-component cou-
more preferably isomerize to C’, compared to the vi- pling reaction of aryl or vinyl halides with diarylacety-
nylpalladium species B in Scheme 4. On the other lenes and monosubstituted alkenes can be performed
hand, in the absence of 3, C may undergo the second under palladium catalysis to selectively give the corre-
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Table 4. Reaction of vinyl bromides 7 with diarylacetylenes 2 and alkenes 3.[a]
[a]
Reaction conditions: [7]:[2]:[3]:[Pd
5 mL) at 1208C under N2 for 2 h.
(OAc)2]:
U
U
G
[b]
[c]
GC yield based on the amount of 7 used. Value in parentheses indicates yield after purification.
In each run, minor amounts of Mizoroki–Heck-type product and fulvene derivative were also formed, but their exact
yields were not determined.
[d]
1
Determined by H NMR.
Table 5. Reaction of vinyl bromides 7 with diarylacetylenes 2.[a]
[a]
Reaction conditions: [7]:[2]:[Pd
N
[NaHCO3]=1:2:0.05:2 (in mmol), in DMF (5 mL) under N2 at 1208C.
[b]
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Palladium-Catalyzed Intermolecular Three-Component Coupling of Organic Halides
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Scheme 5. A plausible mechanism for the reaction of 7 with 2 in the presence or absence of 3.
also been presented. The present catalytic system has
appeared to be useful for the 1:2 coupling of vinyl
bromides with diarylacetylenes to produce pentaaryl-
fulvenes.
Experimental Section
General Remarks
The 1H and 13C NMR spectra were recorded at 400 or
270 MHz and 100 or 68 MHz, respectively, for CDCl3 solu-
tions. MS data were obtained by EI, unless noted. GC analy-
sis was carried out using a silicon OV-17 column (i. d.
2.6 mm”1.5 m) or a CBP-1 capillary column (i. d. 0.5 mm”
25 m). GC-MS analysis was carried out using a CBP-1 capil-
lary column (i. d. 0.25 mm”25 m).
Bromides 7b–h and 11[11b] and diarylacetylenes 2b–d[15]
and 2e[16] were prepared by the methods reported previously.
Other starting materials were commercially available. Char-
acterization data of all the products are reported in the Sup-
porting Information.
Scheme 6. Syntheses of 12 and 13 from 6a. Reaction condi-
tions: [a] i) NaOH (4 equivs.), MeOH, 808C, 6 h; ii) NBS
(1.2 equivs.), NEt3 (20 mol%), MeCN/H2O (99:1), room
temperature, 5 min. [b] See footnote[a] in Table 4. [c] See
footnote[a] in Table 5.
The following experimental procedures may be regarded
as typical in methodology and scale.
Palladium-Catalyzed Reaction of 4-Iodotoluene (1b)
with Diphenylacetylene (2a) and Butyl Acrylate (3a)
(entry 10 in Table 1)
sponding 1:1:1 coupling products. The reaction pro-
vides a straightforward route to arylated oligoenes,
which are of interest for their photo- and electro-
chemical and biological properties.[14] A further ho-
mologation method of the oligoene chain of the
A mixture of 4-iodotoluene (1b) (1 mmol, 218 mg), dipheny-
lacetylene (2a) (4 mmol, 712 mg), butyl acrylate (3a)
(1 mmol, 128 mg), Pd(OAc)2 (0.05 mmol, 11 mg), LiCl
G
(0.7 mmol, 30 mg), NaHCO3 (2 mmol, 168 mg), and 1-meth-
ylnaphthalene (ca. 60 mg) as internal standard was stirred in
three-component products by a simple procedure has DMF/H2O (5 mL, 9:1) under nitrogen at 1308C. After 1 h,
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Kana Shibata et al.
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the reaction mixture was poured into ether (70 mL), washed
by water (100 mL, three times), and dried over sodium sul-
fate. GC and GC-MS analyses confirmed the formation of 4
and 5 in 72 and 12% yields, respectively. The product 4
(197 mg, 50%) was isolated by column chromatography on
silica gel using hexane-ethyl acetate (99.5:0.5, v/v) as eluant.
Although the NMR spectra of 4 indicated that it consists of
Li, Z. Zhang, J. Org. Chem. 2005, 70, 1712; g) W. S.
Cheung, R. J. Patch, M. R. Player, J. Org. Chem. 2005,
70, 3741; h) R. Yanada, S. Obika, T. Inokuma, K.
Yanada, M. Yamashita, S. Ohta, Y. Takemoto, J. Org.
Chem. 2005, 70, 6972.
[3] Intermolecular reaction with organoboron reagents:
a) A. N. Thadani, V. H. Rawal, Org. Lett. 2002, 4, 4317;
b) C. Zhou, D. E. Emrich, R. C. Larock, Org. Lett.
2003, 5, 1579; c) X. Zhang, R. C. Larock, Org. Lett.
2003, 5, 2993; d) C. Zhou, R. C. Larock, J. Org. Chem.
2005, 70, 3765.
[4] Intermolecular reaction with terminal alkynes: a) M.
Pal, K. Parasuraman, V. Subramanian, R. Dakarapu,
K. R. Yeleswarapu, Tetrahedron Lett. 2004, 45, 2305;
b) L. R. Pottier, J.-F. Peyrat, M. Alami, J.-D. Brion,
Synlett 2004, 1503; c) M. Shi, L.-P. Liu, J. Tang, Org.
Lett. 2005, 7, 3085.
two geometrical isomers [(2E,4E):(2E,4Z)=1.2:1], the
A
minor isomer could be isolated by recrystallization from
hexane after the column chromatographic separation and
was determined to possess (2E,4Z)-geometry by NOE ex-
periments (see the Supporting Information).
Compound 4 [(2E,4E):
(2E,4Z)=1.2:1]:[7a] oil; 1H NMR
G
(400 MHz, CDCl3): d=0.87–0.91 (m, 3H), 1.25–1.36 (m,
2H), 1.53–1.58 (m, 2H), 2.20 (s, 3H, 4Z), 2.39 (s, 3H, 4E),
4.04–4.09 (m, 2H), 5.59 (d, J=15.4 Hz, 1H, 4Z), 5.61 (d, J=
15.4 Hz, 1H, 4E), 6.76 (d, J=8.1 Hz, 2H, 4Z), 6.83 (d, J=
8.1 Hz, 2H, 4Z), 6.88–6.90 (m, 2H, 4E), 7.01–7.04 (m, 2H,
4E), 7.08–7.37 (m, 10H), 7.70 (d, J=15.4 Hz, 1H, 4Z), 7.76
(d, J=15.4 Hz, 1H, 4E);13C NMR (100 MHz, CDCl3): d=
13.7 (overlapped), 19.1 (4Z), 19.2 (4E), 21.2 (4Z), 21.3 (4E),
30.68 (4Z), 30.71 (4E), 64.0 (overlapped), 121.3 (4Z), 121.4
(4E), 126.9 (4Z), 127.0 (4E), 127.4 (4E), 128.0 (4Z), 128.10
(4E), 128.12 (4Z), 128.15 (4Z), 128.18(4Z), 128.8 (4E),
130.98 (4Z), 131.03 (overlapped), 131.08 (overlapped),
131.14 (4E), 136.6 (4Z), 136.7 (4E), 137.0 (4Z), 138.2 (4E),
138.5 (4E), 139.0 (4Z), 139.51 (4E), 139.54 (4Z), 141.6 (4Z),
142.1 (4E), 146.4 (4Z), 146.5 (4E), 149.6 (4Z), 149.7 (4E),
167.6 (4Z), 167.7 (4E); MS: m/z=396 (M+); anal. calcd. for
C28H28O2: C 84.81, H 7.12; found: C 84.67, H 7.16.
[5] T. Satoh, S. Ogino, M. Miura, M. Nomura, Angew.
Chem. 2004, 116, 5173; Angew. Chem. Int. Ed. 2004, 43,
5063.
[6] a) K. Kokubo, K. Matsumasa, M. Miura, M. Nomura, J.
Org. Chem. 1996, 61, 6941; b) S. Pivsa-Art, T. Satoh, M.
Miura, M. Nomura, Chem. Lett. 1997, 823; c) T. Yasu-
kawa, T. Satoh, M. Miura, M. Nomura, J. Am. Chem.
Soc. 2002, 124, 12680; d) S. Kawasaki, T. Satoh, M.
Miura, M. Nomura, J. Org. Chem. 2003, 68, 6836; e) Y.
Terao, M. Nomoto, T. Satoh, M. Miura, M. Nomura, J.
Org. Chem. 2004, 69, 6942; f) A. Funayama, T. Satoh,
M. Miura, J. Am. Chem. Soc. 2005, 127, 15354.
[7] a) Preliminary communication: K. Shibata, T. Satoh,
M. Miura, Org. Lett. 2005, 7, 1781. After our prelimina-
ry report, heterogeneously catalyzed- and rhodium-cat-
alyzed versions of similar three-component coupling
were reported: b) M. L. Kantam, P. Srinivas, K. B.
Shiva Kumar, R. Trivedi, Cat. Commun. 2007, 8, 991;
c) T. Kurahashi, H. Shinokubo, A. Osuka, Angew.
Chem. 2006, 118, 6484; Angew. Chem. Int. Ed. 2006, 45,
6336.
Acknowledgements
This work was partly supported by a Grant-in-Aid from the
Ministry of Education, Culture, Sports, Science and Technol-
ogy, Japan.
[8] Intermolecular coupling of acetic acid, alkynes, and al-
kenes has been reported: L. Zhao, X. Lu, Org. Lett.
2002, 4, 3903.
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