Palladium-catalyzed carboacylation of alkenes by using acylchromates as acyl donors

Article abstract of DOI:10.1246/bcsj.78.331

Palladium-catalyzed arylacylation of alkenes proceeds by employing acylchromates as acyl donors. When active alkenes such as norbornene and methoxyallene are treated with an aryl iodide, an acylchromate, and a catalytic amount of Pd(OAc)₂/2P(o-Tol)₃, arylacylation of these alkenes proceeds at room temperature. From aryl iodides having an intramolecular alkene moiety, cyclization-acylation products are obtained via intramolecular arylpalladation followed by acylation with acylchromates.

Full text of DOI:10.1246/bcsj.78.331

Ó 2005 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 78, 331–340 (2005)
331
Palladium-Catalyzed Carboacylation of Alkenes by Using
Acylchromates as Acyl Donors
ꢀ
Motoki Yamane, Yuko Kubota, and Koichi Narasaka
Department of Chemistry, Graduate School of Science, The University of Tokyo,
Hongo, Bunkyo-ku, Tokyo 113-0033
Received October 12, 2004; E-mail: narasaka@chem.s.u-tokyo.ac.jp
Palladium-catalyzed arylacylation of alkenes proceeds by employing acylchromates as acyl donors. When active
alkenes such as norbornene and methoxyallene are treated with an aryl iodide, an acylchromate, and a catalytic amount
of Pd(OAc)2/2P(o-Tol)3, arylacylation of these alkenes proceeds at room temperature. From aryl iodides having an in-
tramolecular alkene moiety, cyclization–acylation products are obtained via intramolecular arylpalladation followed by
acylation with acylchromates.
Acyl transition metal complexes play a key role as inter-
mediates of transition metal-catalyzed ketone synthesis.1 There
are three main routes to generate acyl transition metal inter-
mediates. One is the oxidative addition of acyl compounds,
such as acyl halides,2 acid anhydrides,3 esters,4 aldehydes,5
and acyl metals,6 to low valent transition metals. The second
one is the carbonylation of alkylmetals with carbon monox-
ide.7 The last method is the metal exchange between acyl-
metals and transition metal complexes. The former two routes
have been widely applied in the catalytic ketone synthesis,
whereas the last route is not common because few suitable
acylation reagents have been developed. Although some kinds
of acylmetals, such as acylstannanes,8 acylirons9 and acylzir-
coniums,10 are used in palladium(0)-catalyzed preparation of
simple ketones, these acylmetals are unstable in the air or
not so reactive, so heating is required for the transmetalation
step. Particularly, acylsilane has attracted attention as a stable
acyl donor and two types of acylation reactions were devel-
oped recently, although these processes need heating.11
We have been interested in the use of acyl complexes of the
group VI metals as acylation reagents, especially acylchro-
mium compounds.12 Acyl complexes of Group VI metals are
often isolated as air-stable solids and are commonly used as
the precursors of Fischer-type carbene complexes.13 We have
found that the transmetalation between palladium(II) com-
plexes and acylchromates smoothly proceeds in the Pd(0)-cat-
alyzed preparation of aryl and allyl ketones from aryl and allyl
halides (Eq. 1).12a
mediate through oxidative addition. As a communication, we
have briefly reported a palladium-catalyzed arylacylation of
norbornene by using acylchromates as acyl donors.14 In this
paper are explained the details of this palladium-catalyzed
arylacylation of several alkenes including intramolecular reac-
tions.
Results and Discussion
Palladium-Catalyzed Arylacylation of Norbornene. The
palladium-catalyzed arylacylation of norbornene was investi-
gated with phenyl iodide and tetramethylammonium p-
methoxybenzoylchromate 1a in the presence of a catalytic
amount of palladium complexes. Several palladium precata-
lysts such as Pd(PPh3)4 and Pd(dba)2 were examined. Finally,
combinations of Pd(OAc)2 and phosphines gave higher yield
of the arylacylation product; these results are summarized in
Table 1 (Eq. 2).
Table 1. Effect of Solvent and Ligand for Arylacylation of
Norbornene with Acylchromate 1a and PhIaÞ
Yield/%
Entry
Solvent
Ligand
3ad
4ad
1
2
3
4
5
6
7
8
9
toluene
benzene
CH2Cl2
THF
CH3CN
toluene
toluene
toluene
toluene
toluene
toluene
hexane
PPh3
PPh3
PPh3
PPh3
71
54
38
31
14
94
82
80
83
75
5
16
18
45
43
42
—
18
14
9
PPh3
Pd(PPh3)4
(0.01 mol. amt.)
P(o-Tol)3
P(C6H4–p-OMe)3
P(C6H4–p-CF3)3
P(C6H4–3,5-(CF3)2)3
PCy3
O
O
Br
ð1Þ
+
R
Cr(CO)5 NMe4
R
1 atm CO
toluene, rt
1
10
11
12
3
87
17
Arylacylation of unsaturated compounds is recognized as a
convenient way to synthesize various ketones, as exemplified
by the rhodium-catalyzed arylacylation of norbornene with tet-
raphenylborate and acid anhydrides.3a In this reaction acid an-
hydride acts as acyl donor to generate a key acylrhodium inter-
Pt-Bu3
PPh3
63
a) Molar ratio PhI:Norbornene:1a:Pd(OAc)2:Ligand =
5:5:1:0.05:0.1.
Published on the web February 11, 2005; DOI 10.1246/bcsj.78.331

332 Bull. Chem. Soc. Jpn., 78, No. 2 (2005)
Arylacylation of Alkenes
The use of a bulky triarylphosphine, tri-o-tolylphosphine
was found to give the arylacylation product 3ad in 94% yield
without the formation of p-methoxyphenyl phenyl ketone
(4ad) (entry 6). In all the reactions, the arylacylation product
3ad was obtained stereoselectively as the exo-cis adduct.
The scope of this arylacylation of norbornene was examined
with various combinations of acylchromates and aryl iodides
under the above optimized conditions (reaction 3, Table 2).
In most of the cases, arylacylation products 3 were obtained
in high yields. Not only aroylchromates 1a–f (entries 1–7) but
2d
Ph-I
Pd(OAc)2 (0.05 mol. amt.)
Ligand (0.1 mol. amt.)
O
O
+
R
ð2Þ
Ph
R
Ph
rt, 12 h
3ad
4ad
O
NMe4
1a
R = C6H4-p-OMe
R
Cr(CO)5
The reaction in toluene with 0.05 molar amount of
Pd(OAc)2/2PPh3 gave the desired arylacylated norbornene
3ad in 71% yield along with p-methoxyphenyl phenyl ketone
(4ad), the coupling product between phenyl iodide and acyl-
chromate 1a in 16% yield (entry 1). A plausible mechanism
is shown in Scheme 1. Norbornene reacts with phenylpalladi-
um(II) iodide A, generated by oxidative addition of phenyl io-
dide to Pd(0), to give 3-phenylbicyclo[2.2.1]hept-2-ylpalladi-
um(II) intermediate B. A transmetalation between acylchro-
mate 1 and B and a successive reductive elimination affords
arylacylation product 3. Aryl ketone 4 is formed by a reductive
elimination from acyl(aryl)palladium(II) intermediate D,
which is formed by acylation of A with acylchromate 1 with-
out the insertion of norbornene.
The ratio of arylacylation product 3ad and p-methoxyphen-
yl phenyl ketone (4ad) greatly depended on the solvents, and
the yield of arylacylation product 3ad was increased along
with the decrease of the polarity of solvents (entries 1–5).
Acylchromate 1a dissolved completely in polar solvents, while
significant amounts of 1a remained undissolved in nonpolar
solvents at the beginning of the reaction. Due to the low con-
centration of acylchromate 1a in nonpolar solvents, the inser-
tion of norbornene to arylpalladium(II) intermediate A is pre-
ferred over the transmetalation between A and acylchromate
1a (Scheme 1).
Ph
I
2
Pd(0)Ln
Ln
Ph
I
Pd
I
Pd
Ln
Ph
B
A
O
R
Cr(CO)5 NMe4
1a
O
O
Ln
Ph
Pd
R
Pd
Ln
R
Ph
D
C
Pd(0)Ln
O
O
R
Ph
Ph
R
4
3
Scheme 1. Formation of arylacylation product 3 and aryl
ketone 4.
Table 2. Investigation of Acylchromates 1 and Aryl Iodides 2 in Arylacylation of NorborneneaÞ
cat. Pd(OAc)2 /P(o-Tol)3
O
O
Ar-I 2, Acylchromate 1
+
(3)
R
Ar
R
Ar
toluene, rt, 12 h
3
4
Acylchromate 1
Ar–I 2
Yield/%
Entry
R
Ar
3
4
1
2
3
p-MeOC6H4
o-MeOC6H4
p-MeC6H4
Ph
1a
1b
1c
1d
1d
1e
1f
1g
1h
1i
1a
1a
1a
1a
1a
1a
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
2d
3ad
3bd
3cd
3dd
3dd
3ed
3fd
3gd
3gd
3hd
3id
94
90
90
39
79
83
84
38
78
71
98
95
96
89
84
85
4ad
4bd
4cd
4dd
4dd
4ed
4fd
4gd
4gd
4hd
4id
—
—
10
47
8
—
<18
20
8
<13
—
5
2d
2d
2d
2d
2d
2d
2d
2d
2d
2d
2a
2b
2c
2j
4
5bÞ
6
Ph
p-CF3C6H4
2-Furyl
n-Bu
n-Bu
t-Bu
7
8
9bÞ
10
11
12
13
14
15
16
Me
p-MeOC6H4
p-MeOC6H4
p-MeOC6H4
p-MeOC6H4
p-MeOC6H4
p-MeOC6H4
o-MeOC6H4
p-MeC6H4
p-O2NC6H4
p-MeCOC6H4
3aa
3ab
3ac
3aj
4aa
4ab
4ac
4aj
4
8
—
—
2k
3ak
4ak
a) Molar ratio ArI 2:Norbornene:1:Pd(OAc)2:P(o-Tol)3 = 5:5:1:0.05:0.1. b) Reactions were performed in
hexane.

M. Yamane et al.
Bull. Chem. Soc. Jpn., 78, No. 2 (2005)
333
Table 3. Preparation of 3-Acylmethyl-2,3-dihydrobenzo-
furan 10aaÞ
also alkanoylchromates 1g–i (entries 8–11) were available for
this palladium-catalyzed reaction. For the reaction of acylchro-
mates, such as benzoylchromate 1d and pentanoylchromate 1g,
the use of hexane improved the yields of the desired products 3
due to the low solubilities in hexane (entries 4, 5, 8, and 9).
This reaction proceeded smoothly regardless of the substitu-
ents on aryl iodides (entries 12–16).
Vinyl iodide could be employed in the catalytic vinylacyl-
ation of norbornene. From (Z)-1-iodo-2-phenylethene (2l), p-
methoxyphenyl 3-(Z)-2-phenylethenylbicyclo[2.2.1]hept-2-yl
ketone (3al) was obtained in 87% yield with retention of the
Z configuration of the styrene moiety (Eq. 4).
Products
bÞ
Entry
9abÞ
P(o-Tol)3
10a/%
11/%
12 + 13/%
1cÞ
2d,eÞ
3
4
5
6fÞ
1
1
1
1
5
5
0.1
0.1
0.2
1
1
1
45
72
55
58
77
82
6
4
8
23
8
12
8
—
—
—
3
—
a) Molar ratio 1a:Pd(OAc)2 = 1:0.05. Yields are based on 1a.
b) Molar amounts based on 1a. c) The reaction was quenched
after 1 h stirring. d) The reaction was carried out under an
ethene atmosphere. e) 1-p-Methoxyphenylpropan-1-one was
obtained in 22% yield. f) Bis(dibenzylideneacetone)palladi-
um(0) (Pd(dba)2) was used instead of Pd(OAc)2.
Pd(OAc)2 (0.05 mol. amt.)
P(o-Tol)3 (0.1 mol. amt.)
O
ð4Þ
2l , Acylchromate 1a
I
Ph
R
toluene, rt, 12 h
R = C6H4-p-OMe 3al Ph
87%
Norbornadiene reacted with acylchromate 1a and phenyl io-
dide under the same conditions, giving the desired arylacyla-
tion product 5ad in 81% yield (Eq. 5). Non-activated alkenes
such as cyclopentene, styrene, and 1-octene, however, were
found to be inert toward the palladium-catalyzed arylacylation,
and only aryl ketones 4 were obtained.
chromate 1a in the presence of 0.05 molar amount of
Pd(OAc)2 and 0.1 molar amount of P(o-Tol)3 in toluene at
room temperature for 1 h, the cyclized acylation product 3-
(p-methoxybenzoyl)methyl-2,3-dihydrobenzofuran (10a) was
obtained in 45% yield with by-products such as ketones 11,
12, and 13 (entry 1). It was considered that diacylated com-
pounds 12 and 13 were produced via isomerization and/or hy-
droacylation of the allyl part by the action of the palladium(II)
hydride, which was undesirably generated via intramolecular
Heck reaction of allyl o-iodophenyl ether. In fact, the reaction
under ethene atmosphere gave 1-p-methoxyphenylpropan-1-
one in 22% yield based on the acylchromate complex used,
which means hydroacylation of ethene proceeded by palladi-
um(II) hydride generated by the undesired Heck reaction
(entry 2).17 The yield of acylated dihydrobenzofuran 10a
was increased up to about 80% when the reaction was carried
out by the use of an excess amount of allyl o-iodophenyl ether
(9a), and an equimolar amount of P(o-Tol)3 (entries 5 and 6).
Then we tried the reaction of o-iodophenyl 2-methyl-2-pro-
penyl ether 9b, which has no ꢀ-hydrogen participating in the
Heck reaction. As expected, the desired aryl acylated dihydro-
benzofuran 10b was obtained in 86% yield with an equimolar
amount of the substrate 9b (Eq. 8). In addition, o-iodophenyl
ether 9c having an allene part reacted with 1a to give acylated
benzofuran 10c in 96% yield, although 5 molar amounts of 9c
was necessary (Eq. 9).
Pd(OAc)2 (0.05 mol. amt.)
P(o-Tol)3 (0.1 mol. amt.)
O
O
Ph-I 2d, Acylchromate 1a
+
R
ð5Þ
Ph
R
Ph
toluene, rt, 12 h
5ad 81%
4ad 7%
R = C6H4-p-OMe
As allene derivatives are highly reactive toward carbometa-
lation,15 methoxyallene (6)16 reacted with phenyl iodide and
p-methoxybenzoylchromate 1a in the presence of a catalytic
amount of Pd(OAc)2/2P(o-Tol)3. 2,3-Arylacylation product 8
was obtained as an E=Z mixture in 74% yield (Eq. 6).
Pd(OAc)2 (0.05 mol. amt.)
P(o-Tol)3 (0.1 mol. amt.)
Ph
O
Ph-I 2d, Acylchromate 1a
MeO
ð6Þ
MeO
R
toluene, rt, 12 h
6
8 74% (E:Z=4:3)
R = C6H4-p-OMe
Preparation of Acylated Benzofuran and Indole
Derivatives. Then we investigated the intra- and intermolec-
ular arylacylation by using aryl iodides having an alkene moi-
ety at an appropriate position, expecting that intramolecular
arylpalladation might proceed even by employing non-activat-
ed alkenes due to the entropic advantage. The results of the
palladium-catalyzed arylacylation of allyl o-iodophenyl ether
(9a) with acylchromate 1a are summarized in Table 3 (Eq. 7).
Pd(OAc)2 (0.05 mol. amt.)
P(o-Tol)3 (0.1 mol. amt.)
O
I
Acylchromate 1a
ð8Þ
R
O
toluene, rt, 24 h
R = C6H4-p-OMe
O
9b
10b 86%
cat. Pd(OAc)2/P(o-Tol)3
Acylchromate 1a (R = C6H4-p-OMe)
I
Pd(OAc)2 (0.05 mol. amt.)
P(o-Tol)3 (1 mol. amt.)
Acylchromate 1a
O
R
toluene, rt, 24 h
O
9a
I
O
ð9Þ
ð7Þ
O
R
O
O
O
R
R
toluene, rt, 24 h
O
O
R
O
R
10c 96%
R = C6H4-p-OMe
+
+
O
+
9c
O
O
R
This intramolecular arylacylation was nicely applied to
prepare indoline derivatives as summarized in Table 4 (reac-
tion 10).
10a
11
13
12
O
When allyl o-iodophenyl ether (9a) was treated with acyl-

334 Bull. Chem. Soc. Jpn., 78, No. 2 (2005)
Table 4. Preparation of 3-Acylmethylindoline 15aÞ
Arylacylation of Alkenes
cat. Pd(OAc)2/P(o-Tol)3
Acylchromate 1a
(R = C6H4-p-OMe)
O
R
I
(10)
+
N
N
N
R'
toluene, rt, 24 h
14
15
R'
16
R'
SubstratebÞ
R0
Products
bÞ
Entry
P(o-Tol)3
14
15/%
16/%
1
2
3cÞ
14a
COPh
1
1
1
0.1
1
0.1
15a
15b
58
73
70
16a
16b
32
—
21
4
5
14b
CO2Bn
1
5
0.1
1
55
80
29
—
6
14c
14d
Ts
1
0.1
15c
15d
63
16c
16d
19
7dÞ
8
allyl
1
2
0.1
1
63
84
18
3
9
10
14e
CH2Ph
1
5
0.1
0.1
15e
66
92
16e
24
—
a) Molar ratio Acylchromate 1a:Pd(OAc)2 = 1:0.05. Yields are based on 1a. b) Numbers show molar
amounts based on 1a. c) An equimolar amount of 2-methyl-2-butene was added. d) Reactions were carried
out under 1 atm of ethene.
When N-allyl-N-o-iodophenylbenzamide 14a was treated
with acylchromate 1a in the presence of 0.05 molar amount
of Pd(OAc)2 and 0.1 molar amount of P(o-Tol)3 in toluene
Experimental
General. 1H NMR (500 MHz) spectra in CDCl3 were record-
ed on Bruker AM500 and Bruker DRX500 spectrometers using
at room temperature for 24 h, the desired 3-acylmethylindoline
15a was obtained in 58% yield besides 32% yield of a Heck-
CHCl3 as an internal standard (ꢁ ¼ 7:24). 13C NMR (125 MHz)
spectra in CDCl3 were measured with Bruker AM 500 and Bruker
type product, 3-methylindole 16a (entry 1). N-Allyl-2-iodoani-
lines 14b–e, which have an amino protecting group such as
DRX500 spectrometers using CDCl3 as an internal standard
(ꢁ ¼ 77:0). IR spectra were recorded on a Horiba FT 300-S spec-
CO2Bn (entries 5–8), CO2t-Bu (entry 9), tosyl (entry 10), allyl
trophotometer. High-resolution mass spectra were obtained with a
(entries 11–14), or benzyl (entries 15–17), gave acylated indo-
JEOL JMS-SX102A mass spectrometer. Elemental analyses were
line 15b–e in moderate to high yields. In all cases, the use of
an equimolar amount of P(o-Tol)3 suppressed the formation
carried out at The Elemental Analysis Laboratory, Department of
Chemistry, Faculty of Science, The University of Tokyo.
of Heck-type by-product, 3-methylindole 16,18 and increased
Benzene and toluene was distilled from CaCl2, and dried over
Molecular Sieves 4A. Dichloromethane was distilled from P2O5,
then from CaH2, and dried over Molecular Sieves 4A. Acetonitrile
was dried over CaH2 and distilled from P2O5, then from CaH2,
the yields of 3-acylmethylindolines 15 (entries 2, 7, 8, 13,
14, and 16).
From the reaction of acylchromate 1a and N-2-methyl-2-
propenyl-N-o-iodophenylbenzamide 14f, which has no ꢀ-hy-
drogen for the Heck-type reaction, 3-acylmethyl-3-methylin-
doline 15f was obtained in 79% (Eq. 11).
and dried over Molecular Sieves 4A. Tetrahydrofuran (THF)
was purchased in anhydrous form from Kanto Chemical Co.,
Inc. Hexane was distilled. Silica gel column chromatography
was carried out with Merck Art 7734 and Kanto 60N. Preparative
TLC was performed on silica gel (Wakogel B-5F).
Pd(OAc)2 (0.05 mol. amt.)
O
P(o-Tol)3 (0.1 mol. amt.)
Acylchromate 1a
Acylchromate complexes 1a–i,13 (Z)-1-iodo-2-phenylethene,19
and methoxyallene15 were prepared according to the literature pro-
cedure. Norbornene, norbornadiene, phosphine ligands, and aryl
iodides 2a–d, 2j, and 2k were purified by distillation or recrystal-
lization before to use. Pd(OAc)2 and Pd(dba)2 were purchased
from Wako Pure Chemical Industries, Ltd. and Tokyo Kasei
Kogyo Co., Ltd., respectively and used as they arrived. o-Iodo-
phenyl ethers 9a,20 9b,21 9c,22 and o-iodoaniline derivatives
1423,24 were prepared according to literature methods.
All the reactions were carried out under argon atmosphere.
General Procedure of Arylacylation of Alkenes. To a mix-
ture of Pd(OAc)2 (3.7 mg, 0.016 mmol), P(o-Tol)3 (9.9 mg, 0.033
mmol), and acylchromate complex 1 (0.33 mmol) in toluene (1
mL) was added a toluene (1 mL) solution of alkene (1.6 mmol)
I
ð11Þ
R
N
toluene, rt, 24 h
R = C6H4-p-OMe
N
COPh
COPh
15f 79%
14f
Conclusion
Palladium-catalyzed arylacylation of alkenes was developed
by employing acylchromates as acyl donors. Treatment of re-
active alkenes such as norbornene and a 1,2-propadienyl ether
with acylchromate complexes and a catalytic amount of
Pd(OAc)2/2P(o-Tol)3 gave arylacylation products in good
yields. Application of this catalytic arylacylation provides a
preparative method of benzofuran and indoline derivatives.

M. Yamane et al.
Bull. Chem. Soc. Jpn., 78, No. 2 (2005)
335
10:0 Hz, Hi), 3.74–3.78 (1H, m, J ¼ 10:0 Hz, Hj), 3.76 (3H, s,
Hk), 6.68 (2H, d, J ¼ 8:9 Hz, Hl), 6.89–6.91 (1H, m, Hm),
6.92–6.97 (4H, m, Hn), 7.55 (2H, d, J ¼ 8:9 Hz, Ho); 13C NMR
(125 MHz, CDCl3) ꢁ 29.0, 31.1, 37.4, 39.3, 43.5, 54.0, 55.3,
55.7, 113.0, 125.8, 127.6, 128.3, 130.2, 131.5, 141.9, 162.6,
196.8; IR (ZnSe): 700, 836, 1029, 1230, 1257, 1455, 1508,
Hg
Hh
Hc
Hl
Ho
O
Hn
Hj
OCHk
3
Hd
He
Hm
Ha
Hb
NOE
Hf
Hn
Hi
1602, 1662, 2871, 2954 cmꢂ1
.
Ã
Ã
(2R ,3S )-3-p-Methoxyphenylbicyclo[2.2.1]hept-2-yl p-Ni-
trophenyl Ketone (3aj): White solid; mp 135–136 ꢁC; 1H NMR
(500 MHz, CDCl3) ꢁ 1.39–1.51 (3H, m), 1.69–1.74 (2H, m), 2.09–
2.43 (2H, m), 2.66 (1H, s), 3.33 (1H, d, J ¼ 10:1 Hz), 3.77 (3H, s),
3.84 (1H, d, J ¼ 10:1 Hz), 6.71 (2H, d, J ¼ 9:3 Hz), 7.11 (2H, d,
J ¼ 8:8 Hz), 7.56 (2H, d, J ¼ 9:8 Hz), 7.80 (2H, d, J ¼ 9:9 Hz);
13C NMR (125 MHz, CDCl3) ꢁ 29.0, 30.9, 37.2, 39.8, 43.0, 53.5,
55.4, 55.4, 113.4, 112.7, 129.0, 130.2, 131.0, 145.9, 150.1, 163.1,
199.1; IR (ZnSe): 1028, 1171, 1228, 1259, 1342, 1510, 1597,
1666 cmꢂ1; Anal. Found: C, 71.48; H, 6.00; N, 4.00%. Calcd
for C21H21NO4: C, 71.78; H, 6.02; N, 3.99%.
Fig. 1.
and aryl iodide (1.6 mmol). The reaction mixture was stirred at
room temperature for 24 h, filtered through celite, and then solvent
was removed under reduced pressure. The crude material was
purified by preparative TLC (hexane/AcOEt = 3/1 or benzene/
CHCl3 = 3/2), to give arylacylation product.
Physical properties of products are as follows. Relative config-
uration of the compounds 3 having a norbornane structure was es-
timated as exo-cis adduct ((2R ,3S )-bicyclo[2.2.1]heptane struc-
ture) according to the NOESY analysis of 3ad (Fig. 1). All of the
ketones 4 are commercially available.
ꢀ
ꢀ
Ã
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(2R ,3S )-3-p-Acetylphenylbicyclo[2.2.1]hept-2ꢁ-yl
p-Me-
1
thoxyphenyl Ketone (3ak): White solid; mp 121 C; H NMR
(500 MHz, CDCl3) ꢁ 1.38–1.48 (3H, m), 1.66–1.70 (2H, m),
2.40–2.45 (2H, m), 2.42 (3H, s), 2.62–2.65 (1H, m), 3.30 (1H,
d, J ¼ 10:3 Hz), 3.75 (3H, s), 3.82 (1H, d, J ¼ 10:3 Hz), 6.65–
6.70 (2H, m), 7.03–7.06 (2H, m), 7.53–7.56 (4H, m); 13C NMR
(125 MHz, CDCl3) ꢁ 26.4, 29.0, 31.0, 37.2, 39.6, 43.1, 53.8,
55.3, 55.5, 113.2, 127.7, 128.4, 130.2, 131.2, 134.7, 147.9,
162.9, 197.7, 199.5; IR (ZnSe): 1168, 1215, 1228, 1259, 1599,
1674 cmꢂ1; Anal. Found: C, 79.07; H, 7.07%. Calcd for
C23H24O3: C, 79.28; H, 6.94%.
Ã
Ã
p-Methoxyphenyl
(2R ,3S )-3-p-Methoxyphenylbicyclo-
White solid; mp 94–95 ꢁC;
[2.2.1]hept-2-yl Ketone (3aa):
1H NMR (500 MHz, CDCl3) ꢁ 1.34–1.46 (3H, m), 1.64–1.70
(2H, m), 2.35 (1H, s), 2.49 (1H, d, J ¼ 10:1 Hz), 2.64 (1H, s),
3.23 (1H, d, J ¼ 10:1 Hz), 3.61 (3H, s), 3.73 (1H, d, J ¼ 10:1
Hz), 3.78 (3H, s), 6.48 (2H, d, J ¼ 8:7 Hz), 6.70 (2H, d, J ¼
8:8 Hz), 6.80 (2H, d, J ¼ 8:7 Hz), 7.57 (2H, d, J ¼ 8:8 Hz);
13C NMR (125 MHz, CDCl3) ꢁ 29.0, 31.0, 37.2, 39.1, 43.6,
53.2, 55.0, 55.2, 55.7, 112.9, 128.2, 129.2, 130.2, 131.5, 134.1,
157.3, 162.5, 200.2; IR (ZnSe): 1171, 1230, 1512, 1599, 1668
cmꢂ1; Anal. Found: C, 78.47; H, 7.21%. Calcd for C22H24O3:
C, 78.54; H, 7.19%.
Ã
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o-Methoxyphenyl (2R ,3S )-3-Phenylbicyclo[2.2.1]hept-2-
1
yl Ketone (3bd): Colorless oil; H NMR (500 MHz, CDCl3) ꢁ
1.60–1.70 (3H, m), 1.94 (2H, d, J ¼ 7:6 Hz), 2.67 (2H, m), 2.95
(1H, s), 3.44 (1H, d, J ¼ 10:0 Hz), 4.09 (3H, s), 4.23 (1H, d, J ¼
10:0 Hz), 6.92 (2H, t, J ¼ 7:3 Hz), 6.98–7.06 (5H, m), 7.45–7.50
(2H, m); 13C NMR (125 MHz, CDCl3) ꢁ 29.0, 31.1, 37.5, 39.9,
42.9, 53.3, 55.3, 60.5, 110.8, 120.2, 125.6, 127.6, 128.3, 130.1,
130.2, 132.2, 142.5, 157.4, 203.8; IR (ZnSe): 696, 752, 1020,
Ã
Ã
p-Methoxyphenyl
[2.2.1]hept-2-yl Ketone (3ab):
(2R ,3S )-3-o-Methoxyphenylbicyclo-
Colorless oil; 1H NMR (500
MHz, CDCl3) ꢁ 1.41 (1H, d, J ¼ 10:1 Hz), 1.46 (2H, d, J ¼ 6:4
Hz), 1.66–1.74 (2H, m), 2.46–2.48 (2H, m), 2.55 (1H, s), 3.30
(3H, s), 3.49 (1H, d, J ¼ 9:4 Hz), 3.80 (3H, s), 3.90 (1H, d, J ¼
9:4 Hz), 6.40 (1H, d, J ¼ 8:1 Hz), 6.77 (2H, d, J ¼ 8:8 Hz),
6.84 (1H, dd, J ¼ 7:5, 8.1 Hz), 7.00 (1H, dd, J ¼ 7:5, 7.6 Hz),
7.27 (1H, d, J ¼ 7:6 Hz), 7.67 (2H, d, J ¼ 8:8 Hz); 13C NMR
(125 MHz, CDCl3) ꢁ 29.5, 30.9, 36.9, 40.4, 41.2, 45.6, 53.8,
54.2, 55.3, 108.8, 112.8, 120.1, 126.6, 126.9, 130.0, 130.7,
131.7, 155.9, 162.4, 199.9; IR (ZnSe): 1171, 1215, 1240, 1601,
1670 cmꢂ1; Anal. Found: C, 78.39; H, 7.29%. Calcd for
C22H24O3: C, 78.54; H, 7.19%.
(2R ,3S )-3-p-Tolylbicyclo[2.2.1]hept-2-yl p-Methoxyphen-
yl Ketone (3ac): White solid; mp 92–93 ꢁC; 1H NMR (500
MHz, CDCl3) ꢁ 1.34–1.36 (3H, m), 1.65–1.72 (2H, m), 2.11
(3H, s), 2.38 (1H, s), 2.45 (1H, d, J ¼ 10:1 Hz), 2.64 (1H, s),
3.25 (1H, d, J ¼ 10:1 Hz), 3.74 (1H, d, J ¼ 10:1 Hz), 3.77 (3H,
s), 6.70 (2H, d, J ¼ 8:8 Hz), 6.75 (2H, d, J ¼ 7:9 Hz), 6.85
(2H, d, J ¼ 7:9 Hz), 7.58 (2H, d, J ¼ 8:8 Hz); 13C NMR (125
MHz, CDCl3) ꢁ 20.7, 29.1, 31.0, 37.3, 39.3, 43.5, 53.7, 55.2,
55.7, 112.9, 128.1, 128.2, 130.2, 131.6, 135.0, 138.8, 200.1; IR
(ZnSe): 813, 840, 1029, 1170, 1230, 1259, 1417, 1455, 1509,
1600, 1668, 2871, 2954 cmꢂ1; Anal. Found: C, 82.22; H,
7.69%. Calcd for C22H24O2: C, 82.46; H, 7.55%.
1240, 1282, 1597, 1662 cmꢂ1
307.1690. Calcd for C21H22O2 + H: M þ H, 307.1694.
; HR-FABMS: Found: m=z
Ã
Ã
p-Tolyl (2R ,3S )-3-Phenylbicyclo[2.2.1]hept-2-yl Ketone
ꢁ
1
(3cd): White solid; mp 120 C; H NMR (500 MHz, CDCl3) ꢁ
1.35–1.49 (3H, m), 1.65–1.72 (2H, m), 2.28 (3H, s), 2.41 (1H,
s), 2.46 (1H, d, J ¼ 10:3 Hz), 2.66 (1H, s), 3.78–3.81 (1H, m),
4.09–4.12 (1H, m), 6.86–6.94 (5H, m), 6.98–7.02 (2H, m),
7.44–7.47 (2H, m); 13C NMR (125 MHz, CDCl3) ꢁ 21.5, 29.0,
31.1, 37.4, 39.3, 43.4, 53.9, 55.9, 125.7, 127.6, 128.1, 128.3,
128.5, 135.9, 141.8, 142.6, 201.3; IR (ZnSe): 700, 1230, 1606,
1672 cmꢂ1; Anal. Found: C, 86.61; H, 7.83%. Calcd for C21H22O:
C, 86.85; H, 7.64%.
Ã
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Ã
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Phenyl (2R ,3S )-3-Phenylbicyclo[2.2.1]hept-2-yl Ketone
1
(3dd):3a White solid; H NMR (500 MHz, CDCl3) ꢁ 1.40–1.48
(3H, m), 1.65–1.75 (2H, m), 2.44 (1H, s), 2.44–2.47 (1H, m),
2.70 (1H, s), 3.29 (1H, d, J ¼ 10:0 Hz), 3.84 (1H, d, J ¼ 10:0
Hz), 6.90–6.94 (5H, m), 7.18–7.25 (2H, m), 7.32–7.35 (1H, m),
7.52–7.55 (2H, m); 13C NMR (125 MHz, CDCl3) ꢁ 29.0, 31.1,
37.4, 39.1, 43.5, 53.9, 56.2, 125.8, 127.6, 127.9, 128.0, 128.4,
132.0, 138.4, 141.8, 201.7; IR (ZnSe): 1214, 1226, 1448, 1676
cmꢂ1
Phenyl
[2.2.1]hept-2-yl Ketone (3ed):
.
Ã
Ã
p-Methoxyphenyl (2R ,3S )-3-Phenylbicyclo[2.2.1]hept-2-
yl Ketone (3ad):3a White solid; 1H NMR (500 MHz, CDCl3)
ꢁ 1.36–1.39 (1H, m, Ha), 1.41–1.49 (2H, m, Hb and Hc), 1.64–
1.73 (2H, m, Hd and He), 2.38–2.42 (1H, m, Hf), 2.44–2.48
(1H, m, Hg), 2.64–2.68 (1H, m, Hh), 3.24–3.29 (1H, m, J ¼
Ã
Ã
(2R ,3S )-3-p-(Trifluoromethyl)phenylbicyclo-
White solid; mp 124 ꢁC;
1H NMR (500 MHz, CDCl3) ꢁ 1.39–1.54 (3H, m), 1.69–1.74
(2H, m), 2.40–2.44 (2H, m), 2.72 (1H, s), 3.27 (1H, d, J ¼ 10:3

336 Bull. Chem. Soc. Jpn., 78, No. 2 (2005)
Arylacylation of Alkenes
Hz), 3.81 (1H, d, J ¼ 10:3 Hz), 6.87–6.91 (5H, m), 7.45 (2H, d,
J ¼ 8:1 Hz), 7.56 (2H, d, J ¼ 8:1 Hz); 13C NMR (125 MHz,
6.92–6.96 (4H, m), 7.75–7.79 (4H, m); 13C NMR (125 MHz,
CDCl3) ꢁ 55.5, 113.4, 130.7, 132.2, 162.8, 194.5; IR (ZnSe):
CDCl3) ꢁ 28.7, 31.1, 37.4, 38.8, 43.6, 53.7, 56.8, 123.5 (q, JCF
¼
1022, 1165, 1253, 1317, 1602, 1643 cmꢂ1
.
270:9 Hz), 124.8 (q, JCF ¼ 3:6 Hz), 126.0, 127.7, 128.1, 128.3,
133.1 (q, JCF ¼ 32:3 Hz), 141.1, 141.4, 200.9; IR (ZnSe): 771,
1066, 1110, 1118, 1174, 1326, 1670 cmꢂ1; Anal. Found: C,
73.28; H, 5.70%. Calcd for C21H19F3O: C, 73.24; H, 5.56%.
2-Methoxyphenyl 4-Methoxyphenyl Ketone (4ab):26 Color-
less crystal; 1H NMR (500 MHz, CDCl3) ꢁ 3.74 (3H, s), 3.86 (3H,
s), 6.89–6.92 (2H, m), 6.97–7.01 (1H, m), 7.01–7.05 (1H, m),
7.30–7.33 (1H, m), 7.42–7.47 (1H, m), 7.79–7.82 (2H, m);
13C NMR (125 MHz, CDCl3) ꢁ 55.4, 55.6, 111.4, 113.4, 120.4,
129.2, 130.4, 130.6, 131.4, 132.3, 157.0, 163.5, 195.0; IR (ZnSe):
Ã
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2-Furyl (2R ,3S )-3-Phenylbicyclo[2.2.1]hept-2-yl Ketone
(3fd): White solid; mp 81 ꢁC; 1H NMR (500 MHz, CDCl3) ꢁ
1.36–1.50 (3H, m), 1.64–1.71 (2H, m), 2.41–2.45 (1H, m), 2.44
(1H, s), 2.63 (1H, s), 3.32 (1H, d, J ¼ 10:3 Hz), 3.69 (1H, d, J ¼
10:3 Hz), 6.27–6.29 (2H, m), 6.71–6.73 (1H, m), 6.94–7.01 (5H,
m), 7.36–7.38 (1H, m); 13C NMR (125 MHz, CDCl3) ꢁ 28.9,
31.1, 37.7, 38.8, 42.8, 53.6, 56.2, 112.0, 115.7, 125.8, 127.6,
127.9, 141.5, 144.9, 153.5, 190.6; IR (ZnSe): 700, 754, 840,
1012, 1247, 1467, 1567, 1670, 2871, 2954 cmꢂ1; Anal. Found:
C, 80.96; H, 6.96%. Calcd for C18H18O2: C, 81.17; H, 6.81%.
906, 926, 1024, 1147, 1252, 1597, 1653 cmꢂ1
.
4-Methoxyphenyl p-Tolyl Ketone (4ac):27 Colorless crystal;
1H NMR (500 MHz, CDCl3) ꢁ 2.45 (3H, s), 3.95 (3H, s), 6.95 (2H,
d, J ¼ 8:8 Hz), 7.27 (2H, d, J ¼ 8:0 Hz), 7.67 (2H, d, J ¼ 8:0
Hz), 7.81 (2H, d, J ¼ 8:8 Hz); 13C NMR (125 MHz, CDCl3) ꢁ
21.6, 55.4, 113.4, 128.8, 130.0, 130.4, 132.4, 135.4, 142.6,
163.0, 195.3; IR (ZnSe): 757, 1171, 1255, 1597, 1645 cmꢂ1
.
4-Methoxyphenyl Phenyl Ketone (4ad):28 Colorless crystal;
1H NMR (500 MHz, CDCl3) ꢁ 3.87 (3H, s), 6.95 (2H, d, J ¼ 8:9
Hz), 7.42–7.47 (2H, m), 7.52–7.57 (1H, m), 7.71–7.75 (2H, m),
7.83 (2H, d, J ¼ 8:9 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 55.5,
113.5, 128.2, 129.7, 130.1, 131.9, 132.5, 138.2, 163.2, 195.6; IR
Ã
Ã
Butyl (2R ,3S )-3-Phenylbicyclo[2.2.1]hept-2-yl Ketone
(3gd): Colorless oil; 1H NMR (500 MHz, CDCl3) ꢁ 0.65 (3H,
t, J ¼ 7:4 Hz), 0.67–0.78 (1H, m), 0.85–0.95 (2H, m), 1.11–
1.19 (1H, m), 1.20–1.26 (1H, m), 1.30–1.40 (2H, m), 1.55–1.63
(2H, m), 1.65–1.75 (1H, m), 1.84–1.94 (1H, m), 2.26–2.30 (1H,
m), 2.34 (1H, s), 2.50 (1H, s), 2.96 (1H, d, J ¼ 10:2 Hz), 3.14
(1H, d, J ¼ 10:2 Hz), 7.09–7.22 (5H, m); 13C NMR (125 MHz,
CDCl3) ꢁ 13.7, 22.0, 25.1, 28.6, 31.3, 37.3, 38.6, 43.4, 44.1,
52.8, 61.5, 128.1, 128.3, 128.4, 128.5, 211.7; IR (ZnSe): 1456,
1705, 2929, 2954 cmꢂ1; Anal. Found: C, 84.19; H, 9.21%. Calcd
for C18H24O: C, 84.32; H, 9.44%.
(ZnSe): 700, 1147, 1171, 1253, 1281, 1597, 1651 cmꢂ1
.
4-Methylphenyl Phenyl Ketone (4cd):29 Colorless crystal;
1H NMR (500 MHz, CDCl3) ꢁ 2.44 (3H, s), 7.25–7.30 (2H, m),
7.45–7.49 (2H, m), 7.55–7.60 (1H, m), 7.70–7.73 (2H, m),
7.77–7.80 (2H, m); 13C NMR (125 MHz, CDCl3) ꢁ 21.6, 128.2,
128.9, 129.9, 130.3, 132.1, 134.8, 137.9, 143.2, 196.5; IR (ZnSe):
1147, 1255, 1597, 1653 cmꢂ1
Benzophenone (4dd):30
.
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t-Butyl (2R ,3S )-3-Phenylbicyclo[2.2.1]hept-2-yl Ketone
1
Colorless crystal; 1H NMR (500
(3hd): Colorless oil; H NMR (500 MHz, CDCl3) ꢁ 0.84 (9H,
MHz, CDCl3) ꢁ 7.44–7.51 (4H, m), 7.54–7.60 (2H, m), 7.77–
s), 1.26–1.40 (3H, m), 1.56–1.69 (2H, m), 2.25–2.29 (1H, m),
2.36–2.39 (1H, m), 2.50–2.56 (1H, m), 3.06 (1H, d, J ¼ 9:5
Hz), 3.36 (1H, d, J ¼ 9:5 Hz), 6.70–7.21 (5H, m); 13C NMR
(125 MHz, CDCl3) ꢁ 26.0, 29.4, 31.1, 36.7, 42.0, 42.6, 44.3,
53.9, 54.6, 125.9, 127.8, 128.6, 142.9, 216.1; IR (ZnSe): 1074,
1215, 1365, 1454, 1477, 1698, 2952 cmꢂ1; Anal. Found: C,
84.50; H, 9.61%. Calcd for C18H24O: C, 84.32; H, 9.44%.
7.81 (4H, m); 13C NMR (125 MHz, CDCl3) ꢁ 128.3, 130.3,
132.4, 137.6, 196.8; IR (ZnSe): 698, 1276, 1657 cmꢂ1
.
2-Furyl Phenyl Ketone (4fd):31 Colorless oil; H NMR (500
MHz, CDCl3) ꢁ 6.57–6.59 (1H, m), 7.21–7.24 (1H, m), 7.45–7.50
(2H, m), 7.55–7.61 (1H, m), 7.69–7.70 (1H, m), 7.94–7.97 (2H,
m); 13C NMR (125 MHz, CDCl3) ꢁ 112.2, 120.6, 128.4, 129.2,
132.5, 137.2, 147.1, 152.2, 182.5; IR (ZnSe): 870, 1294, 1389,
1
Ã
Ã
Methyl (2R ,3S )-3-Phenylbicyclo[2.2.1]hept-2-yl Ketone
(3id): Colorless oil; 1H NMR (500 MHz, CDCl3) ꢁ 1.19–1.26
(1H, m), 1.32–1.43 (2H, m), 1.49 (3H, s), 1.57–1.67 (2H, m),
2.20–2.24 (1H, m), 2.35–2.37 (1H, m), 2.52–2.56 (1H, m), 2.98
(1H, d, J ¼ 10:3 Hz), 3.19 (1H, d, J ¼ 10:3 Hz), 7.16–7.26
(5H, m); 13C NMR (125 MHz, CDCl3) ꢁ 28.4, 31.1, 31.2, 37.1,
38.4, 43.5, 52.6, 62.5, 126.4, 128.2, 128.4, 142.3, 209.9; IR
(ZnSe): 1169, 1215, 1228, 1259, 1599, 1674 cmꢂ1; Anal. Found:
C, 83.85; H, 8.51%. Calcd for C15H18O: C, 84.07; H, 8.47%.
1461, 1644 cmꢂ1
.
1-Phenylpentan-1-one (4gd):32 Colorless oil; H NMR (500
MHz, CDCl3) ꢁ 0.93 (3H, t, J ¼ 7:4 Hz), 1.40 (2H, tq, J ¼ 7:4,
7.4 Hz), 1.70 (2H, tt, J ¼ 7:4, 7.4 Hz), 2.95 (2H, t, J ¼ 7:4 Hz),
7.40–7.46 (2H, m), 7.50–7.54 (1H, m), 7.92–7.95 (2H, m);
13C NMR (125 MHz, CDCl3) ꢁ 13.9, 22.5, 26.5, 38.3, 128.0,
128.5, 132.9, 137.1, 200.6; IR (KBr): 690, 1448, 1684, 2931,
1
2958 cmꢂ1
.
2,2-Dimethyl-1-phenylpropan-1-one (4hd):33 Colorless oil;
1H NMR (500 MHz, CDCl3) ꢁ 1.33 (9H, s), 7.35–7.40 (2H, m),
7.42–7.46 (1H, m), 7.65–7.70 (2H, m); 13C NMR (125 MHz,
CDCl3) ꢁ 28.0, 44.2, 127.8, 128.0, 130.8, 138.6, 209.3; IR (ZnSe):
Ã
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p-Methoxyphenyl (2R ,3S )-3-(Z)-Styrylbicyclo[2.2.1]hept-
2-yl Ketone (3al):
White solid; mp 123–124 ꢁC; 1H NMR
(500 MHz, CDCl3) ꢁ 1.24–1.43 (3H, m), 1.59–1.70 (2H, m),
2.00–2.05 (1H, m), 2.15–2.17 (1H, m), 2.61–2.63 (1H, m), 2.85
(1H, dd, J ¼ 9:4, 10.0 Hz), 3.48 (1H, d, J ¼ 9:4 Hz), 3.77 (3H,
s), 5.77 (1H, dd, J ¼ 10:0, 15.6 Hz), 6.11 (1H, d, J ¼ 15:6 Hz),
6.79 (2H, d, J ¼ 8:8 Hz), 6.97–6.99 (2H, m), 7.04–7.09 (2H,
m), 7.10–7.14 (1H, m), 7.82 (2H, d, J ¼ 8:8 Hz); 13C NMR
(125 MHz, CDCl3) ꢁ 29.1, 29.4, 35.7, 39.1, 43.7, 52.0, 54.2,
55.3, 113.4, 126.0, 126.8, 128.2, 130.5, 130.5, 131.0, 131.1,
137.5, 162.9, 199.9; IR (ZnSe): 694, 742, 1025, 1112, 1230,
1259, 1417, 1455, 1509, 1600, 1668, 2871, 2952 cmꢂ1; Anal.
Found: C, 82.89; H, 7.38%. Calcd for C23H24O2: C, 83.10; H,
7.28%.
906, 960, 1174, 1192, 1673 cmꢂ1
.
p-Methoxyphenyl (2R ,3S )-3-Phenylbicyclo[2.2.1]hept-5-
Ã
Ã
ꢁ
1
en-2-yl Ketone (5ad): White solid; mp 120–121 C; H NMR
(500 MHz, CDCl3) ꢁ 1.68 (1H, d, J ¼ 8:9 Hz), 2.53 (1H, d, J ¼
8:9 Hz), 2.93 (1H, s), 3.14 (1H, s), 3.20 (1H, d, J ¼ 10:1 Hz), 3.62
(1H, d, J ¼ 10:1 Hz), 3.77 (3H, s), 6.32–6.34 (1H, m), 6.45–6.48
(1H, m), 6.68–6.72 (2H, m), 6.90–6.98 (5H, m), 7.54–7.58 (2H,
m); 13C NMR (125 MHz, CDCl3) ꢁ 45.1, 46.1, 48.7, 49.9, 49.9,
55.3, 113.0, 125.9, 127.7, 128.4, 130.2, 131.6, 138.5, 140.8,
141.0, 162.7, 201.5 cmꢂ1; IR (ZnSe): 1171, 1213, 1255, 1599,
1670 cmꢂ1; Anal. Found: C, 82.84; H, 6.71%. Calcd for
C21H20O2: C, 82.86; H, 6.62%.
Bis(4-methoxyphenyl) Ketone (4aa):25 Colorless crystal; mp
123–124 ꢁC (CHCl3); 1H NMR (500 MHz, CDCl3) ꢁ 3.87 (6H, s),
4-Methoxy-1-p-methoxyphenyl-3-phenylbut-3-en-1-one (8):

M. Yamane et al.
Bull. Chem. Soc. Jpn., 78, No. 2 (2005)
337
This compound was obtained as a mixture of E=Z isomers (4:3).
1
Hz), 6.80 (1H, d, J ¼ 7:9 Hz), 6.87–6.91 (3H, m), 7.11–7.15
(2H, m), 7.90 (2H, d, J ¼ 8:9 Hz); 13C NMR (67.5 MHz, CDCl3)
ꢁ 25.3, 43.8, 47.4, 55.5, 82.8, 109.8, 113.7, 120.5, 122.8, 128.4,
130.2, 130.3, 135.4, 159.0, 163.5, 196.5; IR (ZnSe): 580, 752,
833, 970, 1016, 1167, 1261, 1479, 1599, 1674 cmꢂ1; HR-
FABMS: Found: m=z 283.1334. Calcd for C18H18O3 + H:
M þ H, 283.1335.
Colorless oil; (E)-8 H NMR (500 MHz, CDCl3) ꢁ 3.71 (3H, s),
3.85 (3H, s), 4.10 (2H, s), 6.53 (1H, s), 6.88–6.91 (2H, m),
7.12–7.16 (1H, m), 7.22–7.25 (4H, m), 7.97–8.00 (2H, m);
13C NMR (125 MHz, CDCl3) ꢁ 37.9, 55.4, 60.1, 113.4, 113.6,
125.5, 126.2, 128.4, 130.0, 130.5, 138.9, 146.9, 163.3, 196.3;
(Z)-8 1H NMR (500 MHz, CDCl3) ꢁ 3.67 (3H, s), 3.84 (3H, s),
3.87 (2H, s), 6.14 (1H, s), 6.88–6.91 (2H, m), 7.12–7.16 (1H,
m), 7.22–7.28 (2H, m), 7.45–7.47 (2H, m), 7.92–7.96 (2H, m);
13C NMR (125 MHz, CDCl3) ꢁ 42.0, 55.5, 60.4, 110.2, 113.7,
126.3, 127.8, 128.0, 129.8, 130.6, 137.2, 147.5, 163.4, 196.8; IR
(ZnSe): 694, 1140, 1167, 1205, 1257, 1508, 1574, 1597, 1676
cmꢂ1; Anal. Found: C, 76.29; H, 6.47%. Calcd for C18H18O3:
C, 76.57; H, 6.43%.
General Procedure for Preparation of Acylated Benzo-
furans and Indoles by Catalytic Intra- and Intermolecular
Arylacylation. To a mixture of Pd(OAc)2 (3.7 mg, 0.016 mmol),
P(o-Tol)3 (0.033–0.33 mmol), and acylchromate complex (0.33
mmol) in toluene (1 mL) was added a solution of aryl iodide 9
or 14 (0.33–1.6 mmol) in toluene (1 mL). The reaction mixture
was stirred for 24 h and filtered through celite, then the solvent
was removed under reduced pressure. The crude product was
purified on preparative TLC (hexane/AcOEt = 3/1). By-products
11, 12, and 13 were obtained as a mixture of other products
and were not isolated as pure forms. Spectral data of the starting
materials and products are as follows.
3-(p-Methoxybenzoyl)methylbenzofuran (10c): White sol-
id; mp 91–92 ꢁC; 1H NMR (500 MHz, CDCl3) ꢁ 3.75 (3H, s),
4.18 (2H, s), 6.81–6.84 (2H, m), 7.12 (1H, dd, J ¼ 7:5, 7.5 Hz),
7.18 (1H, dd, J ¼ 7:5, 7.5 Hz), 7.35 (1H, d, J ¼ 7:5 Hz), 7.42
(1H, d, J ¼ 7:5 Hz), 7.50 (1H, s), 7.90–7.93 (2H, m); 13C NMR
(67.5 MHz, CDCl3) ꢁ 33.5, 55.5, 111.5, 113.9, 113.9, 119.7,
122.6, 124.4, 127.9, 129.3, 130.8, 142.9, 155.1, 163.7, 194.8; IR
(ZnSe): 746, 1093, 1169, 1217, 1259, 1452, 1599, 1681 cmꢂ1
;
Anal. Found: C, 76.47; H, 5.41%. Calcd for C17H14O3: C,
76.68; H, 5.30%.
o-Allyloxyphenyl p-Methoxyphenyl Ketone (11): Colorless
1
oil; H NMR (270 MHz, CDCl3) ꢁ 3.87 (3H, s), 4.35 (2H, d, J ¼
9:5 Hz), 5.06 (2H, m), 5.45–5.48 (1H, m), 6.85–7.07 (4H, m), 7.10
(1H, m), 7.54 (1H, m), 7.87 (2H, d, J ¼ 8:9 Hz).
2-[2-(p-Methoxybenzoyl)phenoxy]-1-(p-methoxyphenyl)bu-
tan-1-one (12): Colorless oil; 1H NMR (500 MHz, CDCl3) ꢁ
0.78 (3H, t, J ¼ 13:7 Hz), 1.84 (2H, dq, J ¼ 12:0, 13.7 Hz),
3.82 (3H, s), 3.86 (3H, s), 5.02 (1H, t, J ¼ 12:0 Hz), 6.72 (1H,
d, J ¼ 14:5 Hz), 6.82 (2H, d, J ¼ 15:5 Hz), 6.89–7.23 (4H, m),
7.24–7.30 (1H, m), 7.85 (2H, d, J ¼ 15:5 Hz), 7.97 (2H, d, J ¼
15:5 Hz).
Allyl o-Iodophenyl Ether (9a):20 Colorless oil; 1H NMR (500
MHz, CDCl3) ꢁ 4.58 (2H, d, J ¼ 4:8 Hz), 5.30 (1H, dd, J ¼ 1:4,
10.5 Hz), 5.51 (1H, dd, J ¼ 1:4, 17.3 Hz), 6.04 (1H, ddt, J ¼ 4:8,
10.5, 17.3 Hz), 6.68–6.71 (1H, m), 6.79 (1H, d, J ¼ 8:2 Hz), 7.24–
7.28 (1H, m), 7.76 (1H, dd, J ¼ 1:4, 7.8 Hz); 13C NMR (500 MHz,
CDCl3) ꢁ 69.6, 86.6, 112.4, 117.6, 122.6, 129.3, 132.5, 139.5,
4-[2-(p-Methoxybenzoyl)phenoxymethyl]-1-(p-methoxyphen-
yl)butan-1-one (13): Colorless oil; 1H NMR (270 MHz, CDCl3)
ꢁ 1.95 (2H, tt, J ¼ 5:9, 7.3 Hz), 2.68 (2H, t, J ¼ 7:3 Hz), 3.74
(3H, s), 3.85 (3H, s), 4.02 (2H, t, J ¼ 5:9 Hz), 6.80–6.85 (4H,
m), 6.94–7.04 (2H, m), 7.31 (1H, t, J ¼ 8:2 Hz), 7.41 (1H, t, J ¼
8:2 Hz), 7.62–7.71 (4H, m).
157.0; IR (ZnSe): 744, 906, 1016, 1246, 1275, 1469, 1579 cmꢂ1
.
o-Iodophenyl 2-Methyl-2-propenyl Ether (9b):21 Colorless
oil; 1H NMR (500 MHz, CDCl3) ꢁ 1.85 (3H, s), 4.46 (2H, s),
5.00 (1H, s), 5.18 (1H, s), 6.68 (1H, dd, J ¼ 7:5, 7.5 Hz), 6.78
(1H, d, J ¼ 8:1 Hz), 7.25 (1H, dd, J ¼ 7:5, 8.1 Hz), 7.75 (1H,
d, J ¼ 7:5 Hz); 13C NMR (67.5 MHz, CDCl3) ꢁ 19.5, 72.5,
86.5, 112.2, 112.9, 122.5, 129.3, 139.4, 140.2, 157.1; IR (ZnSe):
1
1-p-Methoxyphenylpropan-1-one:34 Colorless oil; H NMR
(500 MHz, CDCl3) ꢁ 1.21 (3H, t, J ¼ 7:3 Hz), 2.96 (2H, q, J ¼
7:3 Hz), 3.87 (3H, s), 6.93 (2H, d, J ¼ 8:8 Hz), 7.96 (2H, d, J ¼
8:8 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 8.4, 31.4, 55.4, 113.6,
130.2, 134.9, 163.3, 199.5.
744, 902, 1016, 1244, 1439, 1469, 1581 cmꢂ1
.
N-Allyl-N-o-iodophenylbenzamide (14a):35
Colorless oil;
o-Iodophenyl 1,2-Propadienyl Ether (9c):22 Colorless oil;
1H NMR (500 MHz, CDCl3) ꢁ 5.36–5.45 (2H, m), 6.78–6.82
(2H, m), 7.05–7.08 (1H, m), 7.24–7.30 (1H, m), 7.75–7.79 (1H,
m); 13C NMR (67.5 MHz, CDCl3) ꢁ 87.2, 90.4, 116.7, 118.3,
124.7, 129.3, 139.6, 156.2, 202.3; IR (ZnSe): 748, 912, 993,
1H NMR (500 MHz, CDCl3) ꢁ 3.85 (1H, dd, J ¼ 7:7, 14.5 Hz),
4.98 (1H, dd, J ¼ 4:9, 14.5 Hz), 5.09–5.15 (2H, m), 5.97–6.15
(1H, m), 6.87 (1H, dd, J ¼ 7:5, 7.5 Hz), 6.99 (1H, d, J ¼ 7:8
Hz), 7.11–7.21 (4H, m), 7.35 (2H, d, J ¼ 7:5 Hz), 7.77 (1H, d,
J ¼ 7:8 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 52.3, 100.1, 118.9,
127.6, 128.3, 128.8, 129.1, 129.7, 131.8, 132.4, 135.7, 140.1,
1018, 1149, 1232, 1336, 1437, 1466, 1579 cmꢂ1
.
3-(p-Methoxybenzoyl)methyl-2,3-dihydrobenzofuran (10a):
White solid; mp 129–130 ꢁC; 1H NMR (500 MHz, CDCl3) ꢁ
3.21 (1H, dd, J ¼ 9:7, 17.8 Hz), 3.47 (1H, dd, J ¼ 4:4, 17.8
Hz), 3.86 (3H, s), 4.04 (1H, dddd, J ¼ 4:4, 6.3, 9.1, 9.7 Hz),
4.18 (1H, dd, J ¼ 6:3, 9.3 Hz), 4.86 (1H, dd, J ¼ 9:1, 9.3 Hz),
6.80 (1H, d, J ¼ 7:8 Hz), 6.84 (1H, dd, J ¼ 7:5, 7.5 Hz), 6.92
(2H, d, J ¼ 8:8 Hz), 7.13 (1H, dd, J ¼ 7:5, 7.8 Hz), 7.18 (1H,
d, J ¼ 7:5 Hz), 7.92 (2H, d, J ¼ 8:8 Hz); 13C NMR (125 MHz,
CDCl3) ꢁ 37.5, 44.1, 55.5, 77.4, 109.7, 113.8, 120.4, 124.3,
128.5, 129.6, 129.9, 130.3, 159.9, 163.7, 196.8; IR (ZnSe):
1169, 1221, 1261, 1483, 1599, 1674 cmꢂ1; Anal. Found: C,
76.26; H, 6.08%. Calcd for C17H16O3: C, 76.10; H, 6.01%.
3-(p-Methoxybenzoyl)methyl-3-methyl-2,3-dihydrobenzo-
144.8, 170.2; IR (ZnSe): 714, 912, 1304, 1377, 1469, 1643 cmꢂ1
.
Benzyl N-Allyl-N-(o-iodophenyl)carbamate (14b):24 Color-
less oil; 1H NMR (500 MHz, CDCl3) ꢁ 3.80 (1H, dd, J ¼ 7:2, 15.0
Hz), 4.58 (1H, dd, J ¼ 5:6, 15.0 Hz), 5.08–5.29 (4H, m), 5.90–
5.99 (1H, m), 6.70 (1H, dd, J ¼ 7:2, 7.2 Hz), 7.15–7.44 (7H,
m), 7.88 (1H, d, J ¼ 7:8 Hz); 13C NMR (125 MHz, CDCl3) ꢁ
52.7, 67.3, 100.4, 118.4, 127.4, 127.7, 128.2, 128.9, 129.1,
130.0, 132.9, 136.4, 139.5, 143.4, 154.7; IR (ZnSe): 725, 1011,
1147, 1215, 1296, 1396, 1471, 1701 cmꢂ1
.
N-Allyl-N-(2-iodophenyl)-p-toluenesulfonamide (14c): Col-
1
orless oil; H NMR (500 MHz, CDCl3) ꢁ 2.44 (3H, s), 4.09 (1H,
dd, J ¼ 7:1, 14.5 Hz), 4.20 (1H, dd, J ¼ 7:1, 14.5 Hz), 4.97 (1H,
d, J ¼ 17:1 Hz), 5.02 (1H, d, J ¼ 10:0 Hz), 5.85 (1H, ddt,
J ¼ 7:1, 10.0, 17.1 Hz), 6.90 (1H, dd, J ¼ 1:2, 7.8 Hz), 7.01
(1H, dd, J ¼ 7:8, 7.8 Hz), 7.24–7.30 (1H, m), 7.29 (2H, d, J ¼
8:1 Hz), 7.66 (1H, d, J ¼ 8:1 Hz), 7.89 (1H, d, J ¼ 7:8 Hz);
1
furan (10b): White solid; H NMR (500 MHz, CDCl3) ꢁ 1.48
(3H, s), 3.17 (1H, d, J ¼ 18:3 Hz), 3.52 (1H, d, J ¼ 18:3 Hz),
3.85 (3H, s), 4.52 (1H, d, J ¼ 9:3 Hz), 4.56 (1H, d, J ¼ 9:3

338 Bull. Chem. Soc. Jpn., 78, No. 2 (2005)
Arylacylation of Alkenes
13C NMR (125 MHz, CDCl3) ꢁ 21.5, 54.5, 103.2, 119.6, 128.1,
128.6, 129.5, 129.8, 130.7, 132.2, 136.2, 140.2, 141.0, 143.7; IR
(ZnSe): 544, 570, 652, 714, 742, 854, 1090, 1161, 1346, 1466
cmꢂ1; Anal. Found: C, 46.35; H, 3.93; N, 3.32%. Calcd for
C16H16INO2S: C, 46.50; H, 3.90; N, 3.39%.
1672 cmꢂ1; HR-FABMS: Found: m=z 422.1425. Calcd for
C24H23NO4 + H: M þ H, 422.1427.
1-Allyl-3-(p-methoxybenzoylmethyl)indoline (15d): Color-
less oil; 1H NMR (500 MHz, CDCl3) ꢁ 3.03 (1H, dd, J ¼ 6:4,
9.3 Hz), 3.21 (1H, dd, J ¼ 9:3, 17.4 Hz), 3.38 (1H, dd, J ¼ 4:8,
12.4 Hz), 3.66–3.70 (3H, m), 3.82–3.85 (4H, m), 5.16 (1H, dd,
J ¼ 1:4, 9.9 Hz), 5.25 (1H, dd, J ¼ 1:4, 17.2 Hz), 5.84–5.91
(1H, m), 6.50 (1H, d, J ¼ 7:3 Hz), 6.67 (1H, dd, J ¼ 7:3, 7.3
Hz), 6.92 (2H, d, J ¼ 8:8 Hz), 7.07–7.10 (2H, m), 7.95 (2H, d,
J ¼ 8:8 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 43.2, 51.5, 55.3,
59.3, 60.2, 107.3, 113.6, 117.3, 117.5, 123.7, 127.7, 129.9,
130.2, 132.8, 133.8, 151.7, 163.4, 197.3; IR (ZnSe): 746, 1165,
1
Diallyl(o-iodophenyl)amine (14d):24 Colorless oil; H NMR
(500 MHz, CDCl3) ꢁ 3.62 (4H, d, J ¼ 6:2 Hz), 5.11 (2H, dd,
J ¼ 1:4, 9.7 Hz), 5.17 (2H, dd, J ¼ 1:4, 17.3 Hz), 5.83 (2H,
ddt, J ¼ 6:2, 9.7, 17.3 Hz), 6.77 (1H, dd, J ¼ 1:1, 7.8 Hz), 7.02
(1H, dd, J ¼ 1:1, 7.8 Hz), 7.27 (1H, dd, J ¼ 1:1, 7.8 Hz), 7.85
(1H, dd, J ¼ 1:1, 7.8 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 56.1,
100.3, 117.7, 124.1, 125.6, 128.4, 134.8, 139.9, 151.7; IR (ZnSe):
644, 723, 758, 918, 991, 1012, 1213, 1415, 1466 cmꢂ1
Allyl(benzyl)o-iodophenylamine (14e):24
Colorless oil;
.
1255, 1597, 1672, 2837 cmꢂ1
; HR-FABMS: Found: m=z
308.1679. Calcd for C20H22NO2 + H: M þ H, 308.1651.
1H NMR (500 MHz, CDCl3) ꢁ 3.57 (2H, d, J ¼ 6:4 Hz), 4.18
(2H, s), 5.11–5.12 (1H, m), 5.13–5.15 (1H, m), 5.82–5.89 (1H,
m), 6.77 (1H, dt, J ¼ 1:4, 7.6 Hz), 7.00 (1H, dd, J ¼ 1:4, 8.0
Hz), 7.19–7.29 (4H, m), 7.37 (2H, d, J ¼ 7:4 Hz), 7.86 (1H, dd,
J ¼ 1:4, 7.8 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 56.1, 56.9,
100.1, 118.1, 124.3, 125.7, 126.9, 128.1, 128.5, 128.8, 134.4,
138.1, 140.0, 151.7; IR (ZnSe): 696, 721, 758, 918, 1012, 1209,
1-Benzyl-3-(p-methoxybenzoylmethyl)indoline (15e): Col-
orless oil; 1H NMR (500 MHz, CDCl3) ꢁ 2.99–3.02 (1H, m), 3.20
(1H, dd, J ¼ 9:3, 17.4 Hz), 3.39 (1H, dd, J ¼ 4:5, 17.4 Hz), 3.66–
3.69 (1H, m), 3.84–3.88 (4H, m), 4.21 (1H, d, J ¼ 14:9 Hz), 4.28
(1H, d, J ¼ 14:9 Hz), 6.53 (1H, d, J ¼ 7:8 Hz), 6.68 (1H, dd,
J ¼ 7:3, 7.3 Hz), 6.91 (2H, d, J ¼ 8:8 Hz), 7.09–7.11 (2H, m),
7.23–7.39 (5H, m), 7.93 (2H, d, J ¼ 8:8 Hz); 13C NMR (125
MHz, CDCl3) ꢁ 36.2, 43.4, 53.1, 55.4, 59.9, 107.1, 113.7,
117.6, 123.8, 127.1, 127.8, 127.9, 128.5, 130.0, 130.3, 132.6,
138.2, 152.2, 163.5, 197.4; IR (ZnSe): 731, 746, 1167, 1217,
1255, 1599, 1672 cmꢂ1; HR-FABMS: Found: m=z 358.1785.
Calcd for C24H23NO2 + H: M þ H, 358.1808.
1468, 1577 cmꢂ1
.
N-(o-Iodophenyl)-N-(2-methylprop-2-enyl)benzamide (14f):24
Colorless oil; 1H NMR (500 MHz, CDCl3) ꢁ 1.86 (3H, s), 3.60
(1H, d, J ¼ 15:0 Hz), 4.79 (1H, s), 4.88 (1H, s), 5.17 (1H, d, J ¼
15:0 Hz), 6.86 (1H, dd, J ¼ 7:8 Hz), 7.09–7.14 (3H, m), 7.16–
7.20 (2H, m), 7.35 (2H, d, J ¼ 8:0 Hz), 7.74 (1H, d, J ¼ 7:8
Hz); 13C NMR (125 MHz, CDCl3) ꢁ 20.9, 54.6, 99.9, 114.0,
127.5, 128.2, 128.6, 129.1, 129.6, 131.4, 136.0, 140.1, 140.4,
144.9, 170.3; IR (ZnSe): 613, 715, 902, 1018, 1290, 1373,
1-Benzoyl-3-( p-methoxybenzoylmethyl)-3-methylindoline
(15f): Colorless oil; 1H NMR (500 MHz, CDCl3) ꢁ 1.32 (3H, s),
3.14 (1H, d, J ¼ 16:7 Hz), 3.39 (1H, d, J ¼ 16:7 Hz), 3.83 (3H, s),
4.01–4.03 (1H, m), 4.18–4.20 (1H, m), 6.86 (2H, d, J ¼ 8:7 Hz),
7.19 (2H, d, J ¼ 7:6 Hz), 7.40–7.46 (5H, m), 7.53 (2H, d, J ¼ 7:2
Hz), 7.82 (2H, d, J ¼ 8:7 Hz); HR-FABMS: Found: m=z
386.1736. Calcd for C25H23NO2 + H: M þ H, 386.1757.
1468, 1577, 1643 cmꢂ1
.
1-Benzoyl-3-(p-methoxybenzoylmethyl)indoline (15a): Col-
1
orless oil; H NMR (500 MHz, CDCl3) ꢁ 3.18 (1H, dd, J ¼ 9:4,
17.7 Hz), 3.43 (1H, dd, J ¼ 4:3, 17.7 Hz), 3.62–3.72 (1H, m),
3.84 (3H, s), 3.93–4.02 (1H, m), 4.39–4.46 (1H, m), 6.85–6.87
(5H, m), 6.90 (2H, d, J ¼ 8:5 Hz), 7.21 (1H, d, J ¼ 7:5 Hz),
7.39–7.42 (2H, m), 7.52 (1H, d, J ¼ 7:5 Hz), 7.89 (2H, d, J ¼
8:5 Hz); IR (ZnSe): 1149, 1257, 1321, 1597, 1653 cmꢂ1; Anal.
Found: C, 77.75; H, 5.85; N, 3.61%. Calcd for C24H21NO3: C,
77.61; H, 5.70; N, 3.77%.
1-Benzoyl-3-methylindole (16a):36 Colorless oil; 1H NMR
(500 MHz, CDCl3) ꢁ 2.24 (3H, s), 7.04 (1H, s), 7.32–7.39 (2H,
m), 7.49–7.59 (4H, m), 7.70 (2H, d, J ¼ 7:7 Hz), 8.37 (1H, d, J ¼
8:0 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 9.7, 116.5, 117.9, 118.9,
123.7, 124.4, 125.0, 128.5, 129.0, 131.6, 131.8, 134.9, 136.3,
168.4; IR (ZnSe): 746, 904, 1215, 1261, 1348, 1450, 1680 cmꢂ1
.
1-Benzoyloxycarbonyl-3-methylindole (16b): Colorless oil;
1H NMR (500 MHz, CDCl3) ꢁ 2.25 (3H, s), 5.42 (2H, s), 7.24–
7.50 (10H, m); 13C NMR (125 MHz, CDCl3) ꢁ 9.6, 68.4, 115.1,
117.3, 118.9, 122.3, 122.7, 124.5, 128.4, 128.6, 128.7, 131.4,
135.3, 150.8; IR (ZnSe): 696, 754, 908, 1026, 1084, 1238,
1350, 1396, 1452, 1724 cmꢂ1; Anal. Found: C, 76.72; H, 5.78;
N, 5.20%. Calcd for C17H15NO2: C, 76.96; H, 5.70; N, 5.28%.
1-Benzoyloxycarbonyl-3-(p-methoxybenzoylmethyl)indoline
(15b): Colorless oil; 1H NMR (500 MHz, CDCl3) ꢁ 3.19 (1H, dd,
J ¼ 9:9, 17.6 Hz), 3.42 (1H, d, J ¼ 17:6 Hz), 3.66–3.70 (1H, m),
3.85 (3H, s), 3.94–3.99 (1H, m), 4.37–4.41 (1H, m), 5.17–5.25
(2H, m), 6.91 (2H, d, J ¼ 8:8 Hz), 6.94–6.98 (1H, m), 7.17
(1H, d, J ¼ 7:4 Hz), 7.22–7.24 (1H, m), 7.30–7.42 (6H, m),
7.94 (2H, d, J ¼ 8:8 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 35.2,
44.7, 54.3, 55.4, 66.9, 113.3, 113.8, 114.9, 122.7, 123.8, 127.5,
128.1, 128.5, 129.6, 130.3, 132.2, 133.7, 136.2, 163.7, 171.1,
196.6; HR-FABMS: Found: m=z 402.1700. Calcd for
C25H23NO4 + H: M þ H, 402.1706.
3-Methyl-1-(p-tolylsulfonyl)indole (16c):37
Colorless oil;
1H NMR (500 MHz, CDCl3) ꢁ 2.24 (3H, s), 2.32 (3H, s), 7.18–
7.23 (3H, m), 7.30 (2H, s), 7.44 (1H, d, J ¼ 7:2 Hz), 7.74 (2H,
d, J ¼ 7:2 Hz), 7.98 (1H, d, J ¼ 7:7 Hz); 13C NMR (125 MHz,
CDCl3) ꢁ 9.7, 21.5, 113.6, 118.6, 119.3, 122.9, 123.0, 124.5,
126.7, 129.7, 131.8, 135.2, 135.4, 144.6; IR (ZnSe): 667, 744,
3-( p-Methoxybenzoylmethyl)-1-( p-tolylsulfonyl)indoline
(15c): Colorless oil; 1H NMR (500 MHz, CDCl3) ꢁ 2.31 (3H, s),
2.67 (1H, dd, J ¼ 9:6, 18.2 Hz), 3.08 (1H, dd, J ¼ 4:4, 18.2 Hz),
3.61 (1H, dd, J ¼ 5:0, 11.2 Hz), 3.69 (1H, dddd, J ¼ 4:4, 5.0, 9.6,
9.9 Hz), 3.83 (3H, s), 4.15 (1H, dd, J ¼ 9:9, 11.2 Hz), 6.88 (2H, d,
J ¼ 8:8 Hz), 6.96–6.99 (1H, m), 7.07 (1H, d, J ¼ 7:4 Hz), 7.15
(2H, d, J ¼ 8:2 Hz), 7.19–7.24 (1H, m), 7.62 (2H, d, J ¼ 8:2
Hz), 7.66 (1H, d, J ¼ 8:1 Hz), 7.76 (2H, d, J ¼ 8:8 Hz); 13C NMR
(125 MHz, CDCl3) ꢁ 21.4, 35.5, 44.1, 55.4, 56.0, 113.7, 115.2,
123.9, 124.5, 127.2, 128.2, 129.3, 129.6, 130.1, 133.8, 134.8,
141.7, 144.0, 163.6, 196.1; IR (ZnSe): 1165, 1257, 1352, 1599,
1119, 1171, 1367, 1446 cmꢂ1
.
1-Allyl-3-methylindole (16d):23 Colorless oil; H NMR (500
MHz, CDCl3) ꢁ 2.33 (3H, s), 4.66 (2H, d, J ¼ 5:4 Hz), 5.08 (1H,
dd, J ¼ 1:2, 17.1 Hz), 5.17 (1H, dd, J ¼ 1:2, 10.3 Hz), 5.98 (1H,
ddt, J ¼ 5:4, 10.3, 17.1 Hz), 6.86 (1H, s), 7.09–7.11 (1H, m),
7.17–7.19 (1H, m), 7.27 (1H, d, J ¼ 8:1 Hz), 7.57 (1H, d, J ¼
7:9 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 9.6, 48.5, 109.3, 110.5,
117.0, 118.6, 119.0, 121.4, 125.4, 128.8, 133.8, 136.3; IR (ZnSe):
1
737, 1188, 1329, 1466, 2916 cmꢂ1
1-Benzyl-3-methylindole (16e):38
.
Colorless oil; 1H NMR

M. Yamane et al.
Bull. Chem. Soc. Jpn., 78, No. 2 (2005)
339
(500 MHz, CDCl3) ꢁ 2.33 (3H, s), 5.24 (2H, s), 6.88 (1H, s), 7.09–
7.12 (3H, m), 7.16 (1H, dd, J ¼ 7:0, 7.0 Hz), 7.23–7.28 (4H, m),
7.58 (1H, d, J ¼ 7:8 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 9.6,
49.7, 109.4, 110.8, 118.7, 119.0, 121.6, 125.8, 126.8, 127.4,
128.7, 128.9, 136.6, 137.9; IR (ZnSe): 737, 1452, 1466, 2916
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cmꢂ1
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