Cross-Coupling of Aryl Halides and Allyl Acetates with Arylboron Reagents in Water Using an Amphiphilic Resin-Supported Palladium Catalyst

Full text of DOI:10.1021/jo982438b

3384
J . Org. Chem. 1999, 64, 3384-3388
Ta ble 1. Cr oss-Cou p lin g of Ar yl Ha lid es w ith Ar ylbor on
Cr oss-Cou p lin g of Ar yl Ha lid es a n d Allyl
Rea gen ts in Wa ter Ca ta lyzed by P a lla d iu m -P h osp h in e
Aceta tes w ith Ar ylbor on Rea gen ts in Wa ter
Usin g a n Am p h ip h ilic Resin -Su p p or ted
P a lla d iu m Ca ta lyst
Com p lexes
yield
entry
aryl halide
C6H5I (4a )
arylboron
catalyst
product
%
1
2
3
5
5
5
5
Pd-PEP (2)
8a
8a
8a
88
80
59
0
Yasuhiro Uozumi,*,† Hiroshi Danjo,†,‡ and
Tamio Hayashi*,‡
Pd-(PEP)2 (3)
Pd/TPPTSa
4
Pd(PPh3)4
8a
5
6
7
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
9a
10a
8a
8a
9a
10a
8a
8b
9b
10b
9a
91
72
84
77
82
70
67
66
80
72
67
85
79
67
70
Faculty of Pharmaceutical Sciences, Nagoya City University,
Mizuho-ku, Nagoya 467-8603, J apan, and Department of
Chemistry, Faculty of Science, Kyoto University, Sakyo,
Kyoto 606-8502, J apan
6
7b
8
NaBPh4
5
6
7
NaBPh4
5
6
7
NaBPh4
5
6
7
C6H5Br (4a ′)
9
10
11b
12c
13
14
15b
16
17
18
19b
Received December 11, 1998
2-CH3C6H4I (4b)
4-CH3C6H4I (4c)
Owing to increasing environmental concerns about
harmful and resource-consuming solvent waste,1 the
chemistry of organic transformations in water is pres-
ently undergoing very rapid growth.2 In addition, the
development of immobilized reagents has been attracting
significant interest for their practical advantages.3 There
is good reason to believe that immobilized catalysts
exhibiting high catalytic activity in aqueous media offer
a viable clean alternative to more traditional methods
of accomplishing many organic reactions. We have re-
cently reported the design and preparation of amphiphilic
resin-supported triarylphosphine-palladium complexes
bound to a poly(ethylene glycol)-polystyrene graft co-
polymer (PEG-PS resin) which exhibit high catalytic
activity in allylic substitution reactions of allyl acetates
with various nucleophiles in aqueous media under mild
reaction conditions.7 As a part of our efforts to develop
the wide utility of these catalysts, we examined the
palladium-catalyzed cross-coupling reaction in water.
We describe herein the arylation of aryl halides and allyl
9a
9c
10c
9a
NaBPh4
a
A catalyst generated in situ by mixing [PdCl(π-C3H5)]2 and
TPPTS (2 mol % Pd, Pd/P ) 1/1) was used. b Without KOH. c Three
mol % Pd of 2 was used.
acetates with arylboron reagents in aqueous media which
is catalyzed by the amphiphilic PEG-PS resin-supported
triarylphosphine-palladium complexes.
The transition-metal-catalyzed cross-coupling of aryl
and alkenyl halides with various organometal reagents
is a useful means of carbon-carbon bond formation. The
palladium-catalyzed cross-coupling using organoboron
reagents, so-called Suzuki-Miyaura coupling, is one of
the representatives.8 Several palladium-phosphine com-
plexes were examined for the coupling reaction of iodo-
benzene with phenylboronic acid in water, the Suzuki-
Miyaura coupling having been well-documented to take
place in aqueous organic media.8 It was found that resin-
supported palladium-phosphine complexes catalyze the
coupling reaction to give biphenyl in high yield. The
PEG-PS resin-supported palladium-monophosphine com-
plex Pd-PEP9 (2) was readily prepared by treatment of
resin-supported phosphine 17a with an excess amount of
di(µ-chloro)bis(η3-allyl)dipalladium(II) ([PdCl(η3-C3H5)]2)
(Pd/P > 1/1) followed by removal of unimmobilized [PdCl-
(η3-C3H5)]2 by washing three times with chloroform
(Scheme 1). The gel-phase 13C{1H} NMR of 2 exhibited
a singlet signal at 61.4 ppm and two doublet signals at
80.0 ppm (2J C-P ) 31 Hz) and 118.3 ppm (2J C-P ) 5 Hz),
demonstrating that its structure is PdCl(η3-allyl)(phos-
phine).10 A mixture of iodobenzene (4a ) and phenylbo-
ronic acid (5) was agitated in water with shaking on a
wrist-action shaker in the presence of 4.5 equiv of
potassium hydroxide and 2 mol % palladium of Pd-PEP
complex 2 at 25 °C for 24 h to give biphenyl 8a in 88%
yield (Table 1, entry 1, and Scheme 2). The coupling with
† Nagoya City University. Address correspondence to this author.
FAX: (+81)-52-836-3435. E-mail: uo@phar.nagoya-cu.ac.jp.
‡ Kyoto University.
(1) For example, see: Anastas, P. T., Williamson, T. C., Eds.; Green
Chemistry; ACS Symposium Series 626; American Chemical Society:
Washington: DC, 1996, and references therein.
(2) For recent reviews, see: (a) Li, C.-J .; Chan, T.-H. Organic
Reactions in Aqueous Media; Wiley: New York, 1997. (b) Grieco, P.
A., Ed.; Organic Synthesis in Water; Kluwer Academic Publishers:
Dordrecht, 1997.
(3) For recent reviews, see: (a) Bunin, B. A. Combinatorial Index;
Academic Press: London, 1998; p 262. (b) Obrecht, D.; Villalgordo, J .
M. Solid-Supported Combinatorial and Parallel Synthesis of Small-
Molecular-Weight Compound Libraries; Tetrahedron Organic Chem-
istry Series Vol. 17, Elsevier: Oxford, 1998; p 44.
(4) For a review, see: Herrmann, W. A.; Kohlpaintner, C. W. Angew.
Chem., Int. Ed. Engl. 1993, 32, 1524-1544.
(5) For recent examples of reactions catalyzed by palladium-
phosphine complexes performed in aqueous media, see: (a) Geneˆt, J .
P.; Blart, E.; Savignac, M. Synlett 1992, 715. (b) Geneˆt, J . P.; Blart,
E.; Savignac, M.; Lemeune, S.; Paris, J .-M. Tetrahedron Lett. 1993,
34, 4189. (c) Lemaire-Audoire, S.; Savignac, M.; Blart, E.; Pourcelot,
G.; Geneˆt, J . P. Tetrahedron Lett. 1994, 35, 8783. (d) Geneˆt, J . P.; Blart,
E.; Savignac, M.; Lemeune, S.; Lemaire-Audoire, S.; Paris, J .-M.;
Bernard, J .-M. Tetrahedron 1994, 50, 497. (e) Blart, E.; Geneˆt, J . P.;
Safi, M.; Savignac, M.; Sinou, D. Tetrahedron 1994, 50, 505. (f)
Amatore, C.; Blart, E.; Geneˆt, J . P.; J utand, A.; Lemaire-Audoire, S.;
Savignac, M. J . Org. Chem. 1995, 60, 6829. (g) Lemaire-Audoire, S.;
Savignac, M.; Dupuis, C.; Geneˆt, J . P. Tetrahedron Lett. 1996, 37, 2003.
(h) Bumagin, N. A.; Bykov, V. V.; Sukhomlinova, L. I.; Tolstaya, T. P.;
Beletskaya, I. P. J . Organomet. Chem. 1995, 486, 259.
(8) For a review, see: Miyaura, N.; Suzuki, A. Chem. Rev. 1995,
95, 2457.
(9) The abbreviation PEP comes from PEG-PS resin (PE)-supported
phosphine (P).
(10) The values of the coupling constants are in the typical range
for PdCl(η3-allyl)(phosphine) complexes. For recent relevant papers on
NMR studies of π-allylpalladium complexes, see: (a) Hayashi, T.;
Kawatsura, M.; Uozumi, Y. J . Am. Chem. Soc. 1998, 120, 1681. (b)
Pregosin, P. S.; Salzman, R.; Togni, A. Organometallics 1995, 14, 842.
(6) Very recently, Bergbreiter and Liu have reported water-soluble
polymer-bound, recoverable palladium(0)-phosphine catalysts; see:
Bergbreiter, D. E.; Liu, Y.-S. Tetarhedron Lett. 1997, 38, 7843.
(7) (a) Uozumi, Y.; Danjo, H.; Hayashi, T. Tetrahedron Lett. 1997,
38, 3557. (b) Uozumi, Y.; Danjo, H.; Hayashi, T. Tetrahedron Lett. 1998,
39, 8303.
10.1021/jo982438b CCC: $18.00 © 1999 American Chemical Society
Published on Web 04/14/1999

Notes
J . Org. Chem., Vol. 64, No. 9, 1999 3385
Sch em e 1
transformation,8,13 while immobilization of catalysts often
causes decrease of catalytic activity in general. The
reaction of o- and p-iodotoluene (4b and 4c) with 5-7
gave the corresponding biaryls under the same reaction
conditions in 66-85% yield (entries 12-19).
Sch em e 2
Encouraged by the results obtained in the Suzuki-
Miyaura coupling, we examined the application of Pd-
PEP (2) to the allylic arylation using arylboron reagents.
Compared to the significant development of the Suzuki-
Miyaura coupling, rather surprisingly only scattered
attention has been paid to the use of arylboron reagents
for the arylation of allyl alcohol derivatives.14 In particu-
lar, only a few works on the catalytic allylic arylation of
1,3-disubstituted secondary allyl esters have been re-
ported so far.15 Recently, Kobayashi et al. have developed
nickel-catalyzed arylation of allylic carbonates with
lithium organoborates.16 It was found that Pd-PEP
complex 2 catalyzes allylic arylation of secondary and
primary allyl acetates with arylboronic acid and sodium
tetraphenylborate at 25 °C in water (Scheme 3). The
results obtained are summarized in Table 2, which also
includes those obtained with triphenylphosphine and
TPPTS11 for comparison. A mixture of cinnamyl acetate
11a , phenylboronic acid (1.5 equiv), and potassium
carbonate (4.5 equiv) in water was shaken in the presence
of 2 mol % palladium of Pd-PEP 2 at 25 °C for 24 h to
give 99% yield of 1,3-diphenylpropene (12a ) (Table 2,
entry 1). The resin-supported catalyst was readily recov-
ered by simple filtration and could be taken on to the
next series of the reaction. Thus, after completion of the
reaction, the resin-supported catalyst was washed twice
with THF and water under nitrogen atmosphere in the
Merrifield vessel. To the reaction vessel were charged
aqueous potassium carbonate, allyl acetate 11a , and
phenylboronic acid (5), and the entire mixture was
agitated under the same reaction conditions to give 80%
yield of 12a . The allylic arylation with sodium tetraphen-
ylborate took place to give 99% yield of 12a (entry 3).
The Pd-PEP showed much lower catalytic activity in
resin-supported palladium-bis(triarylphosphine) com-
plex 3 (Pd-(PEP)2)7a gave 80% yield of 8a (entry 2). The
cross-coupling using water-soluble phosphine ligand
TPPTS11,12 showed lower catalytic activity under the
reaction conditions giving 59% yield of 8a (entry 3).
Palladium-triphenylphosphine complex did not catalyze
the reaction in water owing to its insolubility (entry 4).
The arylation with 4-methylphenylboronic acid (6) and
4-methoxyphenylboronic acid (7) gave biaryls 9a and 10a
in 91% and 72% yields, respectively, under the same
reaction conditions (entries 5 and 6). The coupling
reaction of 4a with sodium tetraphenylborate took place
without base to give 84% of 8a . Bromobenzene (4a ′) also
underwent the cross-coupling with arylboron reagents at
25 °C by use of Pd-PEP catalyst in water. The reaction
of 4a ′ with 5, 6, and 7 gave biaryls 8a , 9a , and 10a in
77%, 82%, and 70% yield, respectively (entries 8-10). It
has been well-documented that Suzuki-Miyaura cou-
pling of aryl halides with arylboronic acids catalyzed by
palladium-phosphine complexes requires a reaction
temperature around 80 °C even for aryl iodides.8 This
immobilized Pd-PEP (2) shows catalytic activity in water
higher than that of other homogeneous palladium-
phosphine complexes so far reported for the present
(14) (a) Miyaura, N.; Yamada, K.; Suginome, H.; Suzuki, A. J . Am.
Chem. Soc. 1985, 107, 972. (b) Moreno-Man˜as, M.; Pajuelo, F.; Pleixats,
R. J . Org. Chem. 1995, 60, 2396.
(15) Palladium-catalyzed arylation of 1,3-diphenyl-2-propenyl ac-
etate and 2-cyclohexenyl acetate with sodium tetraphenylborate has
been reported; see: Legros, J .-Y.; Fiaud, J .-C. Tetrahedron Lett. 1990,
31, 7453.
(16) (a) Kobayashi, Y.; Mizojiri, R.; Ikeda, E. J . Org. Chem. 1996,
61, 5391. (b) Kobayashi, Y.; Takahisa, E.; Usmani, S. B. Tetrahedron
Lett. 1998, 39, 597. (c) Usmani, S. B.; Takahisa, E.; Kobayashi, Y.
Tetrahedron Lett. 1998, 39, 601.
(11) TPPTS ) triphenylphosphinetrisulfonate sodium salt. Sinou,
D. Bull. Soc. Chim. Fr. 1987, 3, 480.
(12) Casalnuovo, A. L.; Calabrese, J . C. J . Am. Chem. Soc. 1990,
112, 4324.
(13) Very recently, highly reactive systems in which Suzuki-
Miyaura coupling is promoted at ambient temperature have been
developed; see: (a) Anderson, J . C.; Namli, H.; Roberts, C. A.
Tetrahedron, 1997, 53, 15123. (b) Albisson, D. A.; Bedford, R. B.;
Lawrence, S. E.; Scully, P. N. Chem. Commun. 1998, 2095.

3386 J . Org. Chem., Vol. 64, No. 9, 1999
Notes
Sch em e 3
Sch em e 4
and 3-acetoxy-4-methyl-1-phenylpentene (11e) also un-
derwent the alkylation to give 12c, 12d , and 12e in 94%,
85%, and 81% yield, respectively (entries 10-13). The
Pd-PEP catalyst is also effective for the arylation of
2-cyclohexenyl acetate (14) in aqueous potassium carbon-
ate to give 3-phenylcyclohexene (15) in 90% yield (entry
14).
Ta ble 2. Ar yla tion of Allylic Aceta tes in Wa ter
Ca ta lyzed by P d -P EP (2)a
allyl
yield
The Pd-PEP catalyzed arylation was found to proceed
with inversion of configuration with respect to the
stereogenic carbon center where the arylation took place.
Thus, the reaction of cis-3-acetoxy-5-carbomethoxy-1-
cyclohexene (16) with phenylboronic acid in the presence
of Pd-PEP (2 mol % of Pd) and potassium carbonate in
water at 25 °C gave 3-phenyl-5-carbomethoxy-1-cyclo-
hexene (17) in 45% yield as a single diastereoisomer
(Table 2, entry 15). The chemical yield of arylation was
improved by use of sodium tetraphenylborate to 96%
without loss of stereoselectivity (entry 16). The stereo-
chemistry of 17 was assigned to be trans by comparison
of the 1H NMR spectrum with reported data (Scheme 4).17
This catalytic arylation must proceed via the π-allylpal-
ladium intermediate 18, which is formed by the oxidative
addition of allylic acetates to a palladium(0) species. The
stereochemistry upon oxidative addition to palladium(0)
complexes coordinated with phosphine ligands has been
reported to be inversion with allylic acetates.18 It is
deduced from the overall inversion of configuration
observed here in the catalytic arylation that the stereo-
chemistry upon arylation of π-allylpalladium is retention,
indicating that the aryl group attacks the palladium atom
of the π-allylpalladium intermediate to form the π-allyl-
(aryl)palladium intermediate 19 and reductive elimina-
tion gives the allylarene 17. The inversion of configura-
tion at catalytic allylic arylation has been also observed
in the nickel-catalyzed arylation of allylic carbonates with
lithium arylborate.16a
entry acetate reagent
catalyst
product
(%)
1
2
11a
11a
11a
11a
11b
11b
11b
11b
11b
11c
11c
11d
11e
14
5
5
Pd(PEP) (2)
Pd(PEP)2 (3)
12a
12a
12a
12a
12b
12b
12b
12b
12b
12c
12c
12d
12e
15
99
80
99
29
99
15
3b
4c
5
NaBPh4
5
5
5
5
5
NaBPh4
5
NaBPh4
5
NaBPh4
5
2
2
2
6
Pd/TPPTSd
)
7e
8f
9b
Pd(PPh3 4
no reaction
Pd(PPh3)4
14g
99
90
94
85
81h
90
45
96
2
2
2
2
2
2
2
2
10
11b
12
13b
14
15
16
16
5
17
17
16b
NaBPh4
a
All reactions were carried out in the presence of 2 mol % Pd
b
of catalyst at 25 °C for 24 h, unless otherwise noted. Without
K2CO3. c Carried out in aqueous benzene solvent (H2O/benzene )
d
1.0/5.0). A catalyst generated in situ by mixing [PdCl(π-C3H5)]2
and TPPTS (2 mol % Pd, Pd/P ) 1/1) was used. e At 25 °C in aq.
Na2CO3/benzene (1/5). f Reflux in aqueous Na2CO3/benzene (1/5).
g
h
38% yield of 1-phenylbutadiene (13) was obtained. 10% yield
of regioisomeric product, 1,1-diphenyl-4-methylpent-2-ene, was
obtained.
organic reaction media. The allylic arylation of 11a with
5 in aqueous benzene (H2O/benzene ) 1/5) gave 29% yield
of 12a under otherwise the same reaction conditions
(entry 4). This allylic arylation system using Pd-PEP
catalyst, arylboron reagents, and genuine aqueous reac-
tion media was also successfully applied to other sub-
strates which have substituents on their C1 and C3
positions. Thus, reaction of 1-phenyl-3-acetoxybutene
(11b) with phenylboronic acid was catalyzed by 2 mol %
palladium of Pd-PEP in aqueous potassium carbonate
to give 99% yield of 1,3-diphenylbutene (12b) as a single
regioisomer (entry 5). Palladium-TPPTS complex gener-
ated in situ exhibited much lower catalytic activity under
the present conditions to give 15% yield of 12b (entry 6).
Tetrakis(triphenylphosphine)palladium did not catalyze
the present reaction at 25 °C in aqueous benzene solvent,
and the reaction at higher temperature resulted in the
formation of conjugated 1,3-diene 13 as a major product
(entries 7 and 8). Secondary allylic acetates, 3-acetoxy-
1-phenylpentene (11c), 3-acetoxy-1-phenylnonene (11d ),
Exp er im en ta l Section
Gen er a l. The amphiphilic resin-supported triarylphosphine
1 was prepared on commercially available polystyrene-poly-
ethylene graft copolymer beads, TentaGel S-NH2 (Rapp Poly-
mere, Germany) or ArgoGel NH2 (Argonaut Technologies, CA),
according to the reported procedure.7a Compounds 5-7, and 11a
were purchased from Aldrich Chemical Co. Inc., and 4a , 4a ′,
4b, and 4c were purchased from Wako Chemical Co. Inc. The
agitation of the reaction mixture was performed on a wrist-action
shaker (Burrel Scientific, Inc.). Acetates 14 and 16 were
(17) Sheffy, F. K.; Godschalx, J . P.; Stille, J . K. J . Am. Chem. Soc.
1984, 106, 4833. Also see ref 16a.
(18) Hayashi, T.; Hagihara, T.; Konishi, M.; Kumada, M. J . Am.
Chem. Soc. 1983, 105, 7767.

Notes
J . Org. Chem., Vol. 64, No. 9, 1999 3387
prepared according to the reported procedure.19 Compounds
8a ,b, 9a -c, 10a -c, 11a -c, 11e, 12a -d , and 13-17 are known
compounds.20 Authentic samples of 8a ,b, 9a ,b, and 10a are
commercially available.
ature 135 °C/4 mmHg) gave 2.96 g (78% for two steps) of
3-acetoxy-1-phenylbutene (11b) as a colorless oil: 1H NMR δ
1.25 (d, J ) 6.6 Hz, 3H), 2.07 (s, 3H), 5.53 (quint, J ) 6.6 Hz,
1H), 6.18 (dd, J ) 6.6, 16.1 Hz, 1H), 6.60 (d, J ) 16.1 Hz, 1H),
7.23-7.39 (m, 5H). 3-Acetoxy-1-p h en yl-1-p en ten e (11c):20 1
H
P r ep a r a tion of P a lla d iu m -P EP Com p lex 2. A Merrifield
vessel was charged with 1.04 g of resin-supported phosphine 17a
(loading value, 0.123 mmol/g) and 20 mL of dichloromethane.
To the suspension was added 22.5 mg of di(µ-chloro)bis(η3-allyl)-
dipalladium(II) (0.062 mmol) at room temperature, and the
mixture was shaken on a wrist-action shaker at room temper-
ature for 15 min. After filtration, the resin beads were washed
three times with dichloromethane (20 mL × 3) and dried under
reduced pressure to give 1.06 g of 2: 13C NMR (gel-phase) δ 39.9,
NMR δ 0.94 (t, J ) 7.6 Hz, 3H), 1.73 (dq, J ) 6.9, 7.6 Hz, 2H),
2.08 (s, 3H), 5.34 (dt, J ) 6.9, 7.3 Hz, 1H), 6.12 (dd, J ) 7.3,
16.2 Hz, 1H), 6.60 (d, J ) 16.2 Hz, 1H), 7.24-7.40 (m, 5H).
3-Acetoxy-1-p h en yl-1-n on en e (11d ): 1H NMR δ 0.88 (t, J )
6.8 Hz, 3H), 1.25-1.33 (m, 8H), 1.61-1.76 (m, 2H), 2.07 (s, 3H),
5.39 (dt, J ) 6.6, 7.3 Hz, 1H), 6.12 (dd, J ) 7.3, 16.1 Hz, 1H),
6.60 (d, J ) 16.1 Hz, 1H), 7.22-7.39 (m, 5H); 13C{1H} NMR δ
14.1, 21.3, 22.6, 25.2, 29.1, 31.7, 34.6, 74.8, 126.6, 127.8, 127.9,
128.6, 132.4, 136.5, 170.3. Anal. Calcd for C17H24O2: C, 78.42;
H, 9.29. Found: C, 78.14; H, 9.09. 3-Acetoxy-4-m eth yl-1-
p h en yl-1-p en ten e (11e):20 1H NMR δ 0.95 (d, J ) 6.6 Hz, 3H),
0.97 (d, J ) 6.6 Hz, 3H), 1.96 (octet, J ) 6.6 Hz, 1H), 2.09 (s,
3H), 5.21 (dd, J ) 6.6, 7.6 Hz, 1H), 6.12 (dd, J ) 7.6, 15.8 Hz,
1H), 6.60 (d, J ) 15.8 Hz, 1H), 7.24-7.41 (m, 5H).
Gen er a l P r oced u r e for t h e Allylic Ar yla t ion . Met h od
A: Rea ction of Allyl Aceta tes w ith Ar ylbor on ic Acid s. A
Merrifield vessel was charged with arylboronic acid (0.75 mmol),
potassium carbonate (2.3 mmol), Pd-PEP 2 (0.01 mmol Pd), and
1.5 mL of water. To the mixture was added allyl acetate (0.5
mmol) at ambient temperature, and the reaction mixture was
shaken on a wrist-action shaker at 25 °C for 24 h under nitrogen.
The reaction mixture was filtered, and the resin was extracted
four times with chloroform (6 mL × 4). The combined extract
was dried over Na2SO4 and concentrated under reduced pres-
sure. The residue was chromatographed on silica gel (eluent,
pentane) to give the arylation product.
Meth od B: Rea ction of Ar yl Ha lid es w ith Sod iu m
Tetr a p h en ylbor a te. A Merrifield vessel was charged with
sodium tetraphenylborate (0.75 mmol), Pd-PEP 2 (0.01 mmol
Pd), and 1.5 mL of water. To the mixture was added allyl acetate
(0.5 mmol) at ambient temperature, and the reaction mixture
was shaken on a wrist-action shaker at 25 °C for 24 h under
nitrogen. The reaction mixture was filtered, and the resin was
extracted four times with chloroform (6 mL × 4). The combined
extract was dried over Na2SO4 and concentrated under reduced
pressure. The residue was chromatographed on silica gel (eluent,
pentane) to give the arylation product.
2
2
61.4, 69.7, 70.6, 80.0 (d, J C-P ) 31 Hz), 118.3 (d, jC-P ) 5 Hz),
127.2, 127.7, 128.8, 130.8, 131.6, 132.0, 134.0, 136.5, 166.7; 31
P
NMR (gel-phase) δ 23.2 (s).
Gen er a l P r oced u r e for th e Cr oss-Cou p lin g. Meth od A:
Rea ction of Ar yl Ha lid es w ith Ar ylbor on ic Acid s. A Mer-
rifield vessel was charged with aryl halide (0.5 mmol), arylbo-
ronic acid (0.75 mmol), 1.5 M KOH aqueous solution (1.5 mL),
and Pd-PEP 2 (0.01 mmol Pd), and the mixture was shaken on
a wrist-action shaker at 25 °C for 24 h under nitrogen. The
reaction mixture was filtered, and the resin was extracted four
times with chloroform (6 mL × 4). The combined extract was
dried over Na2SO4 and concentrated under reduced pressure.
The residue was chromatographed on silica gel (eluent, pentane)
to give the coupling product.
Meth od B: Rea ction of Ar yl Ha lid es w ith Sod iu m
Tetr a p h en ylbor a te. A Merrifield vessel was charged with aryl
halide (0.5 mmol), sodium tetraphenylborate (0.75 mmol), 1.5
mL of water, and Pd-PEP 2 (0.01 mmol Pd), and the mixture
was shaken on a wrist-action shaker at 25 °C for 24 h under
nitrogen. The reaction mixture was filtered, and the resin was
extracted four times with chloroform (6 mL × 4). The combined
extract was dried over Na2SO4 and concentrated under reduced
pressure. The residue was chromatographed on silica gel (eluent,
pentane) to give coupling product.
All products in Table 1 were characterized by comparison of
their mass spectra and/or 1H NMR spectra with those of
authentic samples or reported data.20
P r ep a r a tion of Allyl Aceta tes (11b-e). A typical procedure
is given for the preparation of 3-Acet oxy-1-p h en ylb u t en e
(11b).20,21 To a solution of cinnamaldehyde (2.64 g, 20 mmol) in
30 mL of THF was added a 0.87 M solution (THF) of MeMgBr
(34 mL, 30 mmol) at 0 °C, and the entire mixture was stirred
for 2 h. The reaction mixture was diluted with 30 mL of ether
and quenched with a small amount of saturated NH4Cl. The
resulting suspension was filtered through Celite, and the filter
cake was rinsed three times with ether. The combined organic
layer was dried over Na2SO4 and concentrated under reduced
pressure. The residue was chromatographed on silica gel (hex-
ane/EtOAc ) 3/1) to give 1-phenyl-1-buten-3-ol. To a solution of
1-phenyl-1-buten-3-ol in 20 mL of dichloromethane was added
pyridine (5 mL) and acetic anhydride (5 mL) at 0 °C, and the
mixture was stirred at ambient temperature for 2 h. The reaction
mixture was concentrated under reduced pressure, and the
residue was diluted with ether. The mixture was washed with
water and saturated CuSO4 and dried over Na2SO4. After
removal of the solvent, chromatography on silica gel (hexane/
EtOAc ) 10/1) followed by Kugelrohr distillation (pot temper-
Products 12a ,14a 12b,21 12c,22 12d ,23 13,24 15,25 and 1716a were
characterized by comparison of their mass spectra and/or 1H
NMR spectra with those of authentic samples and/or reported
data.20 1,3-Dip h en yl-1-p en ten e (12c): 1H NMR δ 0.91 (t, J )
7.3 Hz, 3H), 1.78-1.89 (m, 2H), 3.31 (quint, J ) 7.3 Hz, 1H),
6.33 (dd, J ) 7.3, 15.8 Hz, 1H), 6.40 (d, J ) 15.8 Hz, 1H), 7.16-
7.35 (m, 10H); 13C{1H} NMR δ 12.3, 28.8, 51.0, 126.1, 126.2,
127.0, 127.7, 128.5, 129.5, 134.2, 137.6, 144.5. Anal. Calcd for
C17H18
: C, 91.84; H, 8.16. Found: C, 91.54, H, 8.46. 1,3-
Dip h en yl-1-n on en e (12d ):22 1H NMR δ 0.86 (t, J ) 7.1 Hz,
3H), 1.24-1.37 (m, 8H), 1.79 (dt, J ) 6.8, 7.3 Hz, 2H), 3.40 (dt,
J ) 7.3, 7.3 Hz, 1H), 6.32 (dd, J ) 7.3, 15.8 Hz, 1H), 6.39 (d, J
) 15.8 Hz, 1H), 7.16-7.35 (m, 10H); 13C{1H} NMR δ 14.1, 22.7,
27.6, 29.3, 31.8, 35.9, 49.2, 126.1, 126.2, 127.0, 127.6, 128.4,
128.5, 129.3, 134.5, 137.7, 144.8. Anal. Calcd for C21H26
: C,
90.59; H, 9.41. Found: C, 90.57; H, 9.36. 1,3-Dip h en yl-4-
m eth yl-1-p en ten e (12e): 1H NMR δ 0.71 (d, J ) 6.6 Hz, 3H),
1.00 (d, J ) 6.6 Hz, 3H), 2.00-2.09 (m, 1H), 3.02-3.07 (m, 1H),
6.38-6.39 (m, 2H), 7.17-7.35 (m, 10H); 13C{1H} NMR δ 20.9,
21.2, 33.2, 57.6, 126.0, 126.1, 127.0, 128.0, 128.4, 128.6, 130.3,
133.2, 137.7, 144.3. Anal. Calcd for C18H20: C, 91.47; H, 8.53.
Found: C, 91.23; H, 8.61. 5-Meth oxyca r bon yl-3-p h en yl-1-
cycloh exen e (17):16a 1H NMR δ 1.97 (ddd, J ) 3.4, 3.9, 13.2
Hz, 1H), 2.16 (ddd, J ) 6.1, 10.5, 13.2 Hz, 1H), 2.33-2.37 (m,
2H), 2.58-2.65 (m, 1H), 3.54-3.60 (m, 1H), 5.76-5.80 (m, 1H),
5.93-5.98 (m, 1H), 7.20-7.33 (m, 5H).
(19) CAS numbers for these compounds are supplied as follows: 8a
[92-52-4]; 8b [643-58-3]; 9a [644-08-6]; 9b [611-61-0]; 9c [613-33-2];
10a [613-37-6]; 10b [92495-54-0]; 10c [53040-92-9]; 11a [103-54-8]; 11b
[74457-38-8]; 11c [113334-98-8]; 11e [108814-27-3]; 12a [3412-44-0];
12b [7302-01-4]; 12c [189322-54-1], [189322-53-0]; 12d [203316-75-
0]; 13 [16939-57-4]; 14 [76704-31-9]; 15 [15232-96-9]; 16 [11518-98-1],
[60729-55-7]; 17 [82342-65-2].
(20) Trost, B. M.; Verhoeven, T. R. J . Am. Chem. Soc. 1980, 102,
5391.
(21) Hayashi, T.; Yamamoto, A.; Hagihara, T. J . Org. Chem. 1986,
51, 723.
(22) Nomura, N.; RajanBabu, T. V. Tetrahedron Lett. 1997, 38, 1713.
(23) Didiuk, M. T.; Morken, J . P.; Hoveyda, A. H. Tetrahedron 1998,
54, 1117.
(24) Matsumoto, Y.; Hayashi, T. Tetrahedron Lett. 1991, 32, 3387.
(25) Moore, W. M.; Salajegheh, A.; Peters, D. G. J . Am. Chem. Soc.
1975, 97, 4954.
Ack n ow led gm en t. The authors are grateful to Dr.
J ohn A. Porco, J r. at Argonaut Technologies for provi-
sion of the PEG-PS resin. This work was supported by
a Grant-in-Aid for Scientific Research, the Ministry of
Education, J apan and “Research for the Future” Pro-
gram, the J apan Society for the Promotion of Science.
Y.U. thanks Shorai Foundation for Science and Tech-

3388 J . Org. Chem., Vol. 64, No. 9, 1999
Additions and Corrections
Su p p or tin g In for m a tion Ava ila ble: 31P{1H} and 13C{1H}
gel-phase NMR spectra of 2. This material is available free of
charge via the Internet at http://pubs.acs.org.
nology and ASPRONC Foundation for partial financial
support of this work. H.D. acknowledges fellowship
support from J apan Society for the Promotion of Science
for J apanese J unior Scientists.
J O982438B
Additions and Corrections
Vol. 63, 1998
Sh en gm in g Ma * a n d Bin Xu . Bicyclic Carbopalladation
Reaction with Two gem-Reaction Centers. Efficient Construction
of Fused Bicyclic Skeletons.
Page 9156. The structures should be numbered as
follows: In eq 2, compounds 12 and 13 should be read
as compounds 5 and 6, respectively. In eq 3, compounds
14 and 15 should be read as compounds 7 and 8,
respectively. In eq 4, compounds 16 and 17 should be
read as compounds 9 and 10, respectively. In eq 5,
compounds 18 and 19 should be read as compounds 11
and 12, respectively.
J O994002H
10.1021/jo994022h
Published on Web 04/10/1999