Iridium-catalyzed reaction of 1-naphthols, N-(1-naphthyl)benzenesulfonamides, and salicylaldehyde with internal alkynes

Article abstract of DOI:10.1246/bcsj.74.1727

1-Naphthols efficiently couple with internal alkynes via cleavage of the C-H bond at the peri-position in the presence of a catalyst system of [IrCl(cod)]₂/PBut′₃ to selectively afford the corresponding 8-vinyl-1-naphthol derivatives. N-(1-Naphthyl)benzenesulfonamides can similarly react with the alkynes. The reaction of salicylaldehyde with the alkynes using the catalyst system gives 2-hydroxyphenyl vinyl ketones via cleavage of the aldehyde C-H bond.

Full text of DOI:10.1246/bcsj.74.1727

c. Jpn.
© 2001 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 74, 1727–1735 (2001) 1727
e Chemical
ciety of Ja-
n
e Chemical
ciety of Ja-
n
Iridium-Catalyzed Reaction of 1-Naphthols, N-(1-Naphthyl)benzene-
sulfonamides, and Salicylaldehyde with Internal Alkynes
Iridium-Catalyzed Reaction of 1-Naphthols
Y. Nishinaka et al.
Yuko Nishinaka, Tetsuya Satoh, Masahiro Miura,* Hideaki Morisaka, Masakatsu Nomura,#
Hisaji Matsui,†,## and Chiharu Yamaguchi††
01
27
35
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka, 565-0871
†Collaborative Research Center for Advanced Science and Technology, Osaka University, Suita, Osaka 565-0871
††Research & Development Center, Osaka Gas Co. Ltd., 6-19-9 Trishima, Konohana-ku, Osaka 554-0051
SJA8
09-2673
080
(Received March 12, 2001)
01
1-Naphthols efficiently couple with internal alkynes via cleavage of the C–H bond at the peri-position in the pres-
ence of a catalyst system of [IrCl(cod)]2/PBut3 to selectively afford the corresponding 8-vinyl-1-naphthol derivatives. N-
(1-Naphthyl)benzenesulfonamides can similarly react with the alkynes. The reaction of salicylaldehyde with the alkynes
using the catalyst system gives 2-hydroxyphenyl vinyl ketones via cleavage of the aldehyde C–H bond.
01
.1
The activation of C–H bonds in organic compounds is cur-
rently one of the most significant subjects in organometallic
chemistry1 and transition-metal catalysis.2,3 An effective strat-
egy to regioselectively activate an aromatic C–H bond by tran-
sition-metal complexes is to introduce a functional group hav-
ing ligating ability at an appropriate position of a given aro-
Scheme 1.
matic substrate. Recently, a number of catalytic coupling reac-
tions of aromatic compounds bearing carbonyl or nitrogen-
containing, electronically neutral groups with alkenes or
alkynes involving such a C–H bond activation mode as the key
step have been successfully developed.2,3 Meanwhile, we re-
cently reported that anionic phenol oxygen acts as a good an-
Scheme 2.
chor in some catalytic C–C bond formation reactions via C–H
cleavage.4–8 The reactions of salicylaldehydes with aryl ha-
lides using a palladium catalyst4 and with alkynes using a
rhodium catalyst5 efficiently proceed via cleavage of the alde-
hyde C–H bond to give aryl and vinyl 2-hydroxyphenyl ke-
tones, respectively (Schemes 1 and 2). The former reaction,
that is arylation, can also occur at aromatic C–H bonds under
similar conditions.6 Biphenyl-2-ols and 1-naphthols, for ex-
ample, undergo arylation selectively at the 2ꢀ- and 8-positions,
respectively. The reaction using 1-naphthols (Scheme 3)
seems to be of particular interest, since it has been known to be
difficult to achieve direct C–C coupling at the 8-position of 1-
substituted naphthalenes with good efficiency due to peri-
strain.9 In the light of these results, the coupling of 1-naph-
thols with alkynes was examined. It was found that the reac-
tion with internal alkynes using an iridium catalyst proceeds
efficiently (Scheme 4),10 while rhodium species can not be
used. Furthermore, the reaction of structurally related N-(1-
naphthyl)benzenesulfonamides as well as salicylaldehyde with
the alkynes using iridium species has been undertaken. These
Scheme 3.
results are summarized herein.
Results and Discussion
Reaction of 1-Naphthols. When 1-naphthol (1a) (2
mmol) was treated with 4-octyne (2a) (2 mmol) in the pres-
ence of [IrCl(cod)]2 (0.01 mmol) and Na2CO3 (0.1 mmol) in
refluxing toluene for 2–5 h using a number of monodentate
phosphines as ligands (0.03–0.04 mmol), 8-[(E)-4-octen-4-yl]-
1-naphthol (3) was produced as the single coupling product
(Scheme 4 and Entries 1–4 in Table 1). The product yield was
found to be very sensitive to the identity of the ligands. The
efficiency order was PPh3 ꢀ PCy3 ꢀ P(o-Tolyl)3 < PBut3, in-
dicating that sterically bulky ligands enhance the reaction.
Thus, using PBut3 gave a satisfactory yield of 83% within 2 h.
Increasing the amount of PBut3 to 0.09 mmol did not affect the
# Collaborative Research Center for Advanced Science and Tech-
nology, Osaka University.
## Research & Development Center, Osaka Gas Co. Ltd.

1728 Bull. Chem. Soc. Jpn., 74, No. 9 (2001)
Iridium-Catalyzed Reaction of 1-Naphthols
product yield (Entry 5). The coupling was very sluggish in the
absence of Na2CO3 (Entry 6). While the catalyst system of
[RhCl(cod)]2–dppf–Na2CO3 is effective for the aldehyde-
alkyne coupling in Scheme 2, either this or [RhCl(cod)]2–
PBut3–Na2CO3 was ineffective for the present reaction. Using
[IrCl(cod)]2–dppf–Na2CO3 was obtained only 12% yield of 3.
Various 2-, 4-, or 5-substituted 1-naphthols 1b–1f in place
of 1a also reacted with 2a to give the corresponding coupling
products 4–8 with substantial yields (Entries 7–11). 5-Decyne
(2b) and 2,9-dimethyl-5-decyne (2c) could be used in place of
2a (Entries 12 and 13). Using 2-heptyne (2d) and 1-phenyl-1-
propyne (2e) gave pairs of regioisomers 11/12 and of 13/14,
respectively (Entries 14 and 15). 1-Octyne and 1-trimethylsi-
lyloctyne did not react with 1a, the substrates being recovered.
Reaction of N-(1-Naphthyl)sulfonamides. Sulfonamides
are known to have acidities comparable to phenols.11 Thus, the
amide function may work as effective anchor as well as phe-
nolic oxygen in the catalytic functionalization of aromatic C–
H bonds. Indeed, we reported that both biphenyl-2-ols and N-
(biphenyl-2-yl)sulfonamides react with alkenes at their 2ꢀ-po-
sition in the presence of a palladium–copper catalyst system
under air.12 Consequently, several sulfonamides prepared us-
ing 1-naphthylamine were treated with alkynes under the
present conditions.
amide (15a: X = Cl) with 2a using [IrCl(cod)]2–PBut3–Na2CO3
gave the corresponding 8-substituted product 16 in a yield of
82% (Scheme 5 and Entry 1 in Table 2). In this reaction, P(o-
Tolyl)3 was also effective (Entry 2), although the rate was
Table 1. Reaction of 1-Naphthols (1) with Alkynes 2a)
Time
Entry
1
2
Ligand
Product(s), % yieldb)
/h
5
5
5
2
5
2
4
2
3
2
5
2
2
5
24
c)
1
2
3
4
5
1a
1a
1a
1a
1a
1a
1b
1c
1d
1e
1f
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2b
2c
2d
2e
PPh3
3, 2
3, 64
3, 56
3, 83 (60)
3, 84
c)
P(o-Tolyl)3
c)
PCy3
PBut3
d)
PBut3
6e)
7
8
9
10
11
12
13
14
15
PBut3
PBut3
PBut3
PBut3
PBut3
PBut3
PBut3
PBut3
PBut3
PBut3
3, tr.
4, 70 (48)
5, 93 (42)f)
6, 67 (54)f)
7, 85 (44)f)
8, 82 (42)
9, 73 (41)
10, 75 (61)
11 + 12,g) 89 (59)f)
13 + 14,h) 66 (53)f)
1a
1a
1a
1a
a) The reaction was carried out using 1 (2 mmol), 2 (2
mmol), [IrCl(cod)]2 (0.01 mmol), ligand (0.03 mmol), and
Na2CO3 (0.1 mmol) in refluxing toluene unless otherwise
noted. b) Determined by GLC. Value in parentheses indi-
cates isolated yield. c) Ligand (0.04 mmol) was used. d)
Ligand (0.09 mmol) was used. e) Without Na2CO3. f) Iso-
lated after acetylation with Ac2O in pyridine. g) 11/12 =
62:38. h) 13/14 = 79:21.
The reaction of N-(1-naphthyl)-4-chlorobenzenesulfon-
Scheme 4.
Scheme 5.

Y. Nishinaka et al.
Bull. Chem. Soc. Jpn., 74, No. 9 (2001) 1729
Table 2. Reaction of N-(1-Naphthyl)sulfonamides 15 with
Alkynes 2a)
Time
Entry
15
2
Ligand
Product(s), % yieldb)
/h
2
5
22
3.5
2
2
2
2
2
2
5
c)
1
2
3
15a
15a
15a
15a
15a
15c
15d
15a
15a
15a
15e
2a
2a
2a
2a
2a
2a
2a
2b
2c
2d
2a
PBut3
16, 82 (82)
16, 83
16, 26
c)
P(o-Tolyl)3
c)
PPh3
4d)
5
PBut3
PBut3
PBut3
PBut3
PBut3
PBut3
PBut3
PBut3
16, tr.
17, (77)
18, (92)
19, (81)
20, (67)
21, (75)
22 + 23e), (87)
24, (73)
Scheme 7. Reaction conditions: 25 or 27 (2 mmol), 2a (2
mmol), [IrCl(cod)]2 (0.01 mmol), PBut3 (0.03 mmol), and
Na2CO3 (0.1 mmol), in refluxing chlorobenzene (5 cm3)
for 24 h under N2.
6
7
8
9
10
11
a) The reaction was carried out using 15 (2 mmol), 2 (2
mmol), [IrCl(cod)]2 (0.01 mmol), ligand (0.03 mmol), and
Na2CO3 (0.1 mmol) in refluxing toluene unless otherwise
noted. b) Determined by GLC. Value in parentheses indi-
cates isolated yield. c) Ligand (0.04 mmol) was used. d)
Without Na2CO3. e) 22/23 = 54:46.
Chart 1. Unreactive substrates.
Scheme 6.
somewhat slower than that using PBut3. As in the reaction of
1a, PPh3 was far less effective (Entry 3). Addition of Na2CO3
was also essential for the reaction to take place (Entry 4). 4-
Substituted benzenesulfonamides (15b–15d: X = H, Me,
OMe) and alkynes 2b–2d could be used in place of 15a and
2a, respectively, to afford compounds 17–23 (Entries 5–10).
N-(1-Naphthyl)methanesulfonamide (15e) reacted with 2a
(Scheme 6 and Entry 11) to produce compound 24.
Scheme 8.
Reaction of Related Hydroxy and Amide Compounds.
To determine the applicability of the present catalytic cou-
pling, a number of related compounds were treated with 2a. 4-
Hydroxycoumarin (25) and 4-Hydroxy-1-methyl-2(1H)-qui-
nolone (27) could react with 2a in refluxing chlorobenzene to
give the expected coupling products, 26 and 28, in 70% and
32% yields, respectively (Scheme 7). However, biphenyl-2-ols
(29),6a,6b 2,4,6-trimethylphenol (30),6c N-(biphenyl-2-yl)-4-
chlorobenzenesulfonamide (31),12 and N-benzoyl-1-naphthy-
lamine (32)13 (Chart 1) did not give any coupling products, in
spite of the fact that they undergo palladium-catalyzed aryla-
tion and/or vinylation via C–H cleavage. These results suggest
that for the coupling to take place, an aromatic hydrogen has to
exist at the γ-position, and the coordinating functional group
should be relatively acidic. While the γ-aliphatic hydrogens in
1b and 30 were not attacked, the aldehyde hydrogen in salicyl-
aldehyde (33) was found to be active under the present condi-
tions. Thus, the reaction of 33 with 2a using [IrCl(cod)]2–
PBut3 gave ketone 34 in 90% yield (Scheme 8 and Entry 1 in
Table 3), as did that using [RhCl(cod)]2–dppf.5 However, 1-
Table 3. Reaction of Salicylaldehyde (33) with Alkynes 2a)
Time
Entry
2
Ligand
Product(s), % yieldb)
/h
3
2
2
1
1
1
2
3
4
5
2a
2d
2d
2e
2e
PBut3
PBut3
dppf
34, 90
35, 82; 36, 18
35, 78; 36, 17
37, 47; 38, 43
37, 24; 38, 19
PBut3
dppf
a) The reaction was carried out using 33 (2 mmol), 2 (2
mmol), [IrCl(cod)]2 (0.01 mmol), PBut3 (0.03 mmol) or
dppf (0.02 mmol), and Na2CO3 (0.1 mmol) in refluxing
toluene. b) Determined by GLC.
octyne did not couple with 33, in contrast to the fact that the
reaction using the rhodium catalyst system efficiently takes
place.5 Examinations with unsymmetrical alkynes 2d and 2e
using [IrCl(cod)]2 together with PBut3 or dppf (Entries 2–5) re-

1730 Bull. Chem. Soc. Jpn., 74, No. 9 (2001)
Iridium-Catalyzed Reaction of 1-Naphthols
Scheme 9.
mmol) with 2a (2 mmol) for 1 h gave a mixture of 3 and 16 in
31% and 93% yields, respectively. It should be noted that N-
arylsulfonamides are somewhat more acidic compared with
phenols.11 These results indicate that the acidity of the sub-
strates is one of the important factors determining the reaction
rate.
H–D Exchange Reaction. Murai and co-workers report-
ed that during the ruthenium-catalyzed ortho-alkylation of an
aromatic ketone with an alkene via C–H cleavage, a hydrogen
exchange reaction between the substrates occurs.14 Thus, in
the treatment of acetophenone-d5 with triethoxyvinylsilane, a
part of the deuteriums on the ortho-positions of the ketone is
replaced by the vinyl hydrogens of the alkene accompanied by
deuteration of the alkene. Therefore, they proposed that the
catalytic alkylation consists of reversible steps with the excep-
tion of the last product forming step. Lenges and Brookhart
described that the ketone alkylation also takes place using a
rhodium complex.15 In contrast to the ruthenium catalysis, the
H–D exchange between acetophenone-d8 and trimethylvinylsi-
lane occurs at the meta- and para-positions of the ketone, and
no incorporation of hydrogen is observed at the ortho-posi-
tions.
Fig. 1. Time course of the reaction of 1-naphthols 1 with 4-
octyne (2a); 1a (ꢀ), 1c (ꢁ), 1d (ꢂ), 1e (ꢃ), and 1f (ꢄ).
The reaction was carried out using 1 (2 mmol), 2a (2
mmol), [IrCl(cod)]2 (0.01 mmol), PBut3 (0.03 mmol), and
Na2CO3 (0.1 mmol) in refluxing toluene.
vealed the following: (a) Both PBut3 and dppf can be used in
the iridium catalysis, and (b) the regioselectivity of the reac-
tion depends on the structure of the alkynes used.
Substituent Electronic Effect. In order to examine the
substituent electronic effect on the present coupling, the reac-
tions of 1a and 1c–1f with 2a were monitored periodically by
GC. The conversion of 1 against the reaction time is shown in
Fig. 1. It can be seen that 1c (Y = Cl) and 1e (Z =
NHCOCF3) are consumed faster than 1a, whereas the reactions
of 1d (Y = MeO) and 1f (Z = MeO) are relatively slow. This
indicates that an electron-withdrawing substituent on either the
4- or 5-position on 1-naphthol enhances the reaction. Since
the difference of reaction rates was small in the case of 15, an
equimolar mixture of 15a (X = Cl, 1 mmol) and 15b (X = H,
1 mmol) was treated with 2a (2 mmol) for 1 h. As a result, a
mixture of products 16 (X = Cl) and 17 (X = H) in 84% and
60%, respectively, was obtained. This suggests that an elec-
tron-withdrawing substituent on the benzenesulfonyl moiety
also promotes the reaction to some extent. A competitive reac-
tion using naphthol 1a (1 mmol) and sulfonamide 15a (1
Consequently, we examined the reaction of 1-naphthol (1a)
with styrene-d8 or methanol-d1. While treatment of 1a (1
mmol) with styrene-d8 (2 mmol) in the presence of
[IrCl(cod)]2–PBut3–Na2CO3 in refluxing toluene for 6 h gave
no coupled product, deuterium incorporation into 1a was ob-
served at the 2-, 3-, 4-, and 8-positions (Scheme 9 and Entry 1
1
in Table 4). The deuterium contents estimated by H NMR
were 34, 16, 11, and 70%, respectively. Using methanol-d1 (5
mmol) induced a similar H–D exchange (Entry 5). The ex-
change at the 2- and 8-positions was also observed even at 80
°C (Entry 3). No deuterium incorporation was observed in the
treatment of 1a in the presence of [IrCl(cod)]2 in refluxing tol-
uene-d8. When [RhCl(cod)]2 was used in place of [IrCl(cod)]2,
a)
Table 4. Reaction of 1-Naphthol (1a) with Styrene-d8 or Methanol-d1
Temp.
Time
% D contentc)
Entry
D sourse
M
/°Cb)
140
140
80
/h
6
24
4
4
4
2
3
4
8
1
C8D8
C8D8
Ir
Rh
Ir
Rh
Ir
Rh
34
—
37
48
46
57
49
16
—
—
—
10
8
11
—
—
—
10
—
—
70
—
32
—
47
—
—
2d)
3
CH3OD
CH3OD
CH3OD
CH3OD
CH3OD
4
5
6
7
80
140
140
140
4
4
d)
—
—
a) The reaction was carried out using 1a (1 mmol), C8D8 (2 mmol) or CH3OD (5
mmol), [MCl(cod)]2 (0.01 mmol), PBut3 (0.03 mmol), and Na2CO3 (0.1 mmol) in
1
toluene. b) Bath temperature. c) Determined by H NMR using methyl cyclo-
hexanecarboxylate as internal standard. d) Monitored by GC-MS. d) Without
metal species.

Y. Nishinaka et al.
Bull. Chem. Soc. Jpn., 74, No. 9 (2001) 1731
no detectable H–D exchange occurred in the case of styrene-d8
the bulkiness.
(Entry 2).
With methanol-d1 in the presence of the
The H–D exchange reaction of 1a with styrene-d8 suggests
that the alkene reacts with complex B to form an alkylarylirid-
ium species and the insertion is reversible. The fact that no
coupling product is formed is attributable to the high barrier of
reductive elimination. Deuteration at the 2-position may imply
the formation of 1-naphthyl-OD, possibly via H–D exchange
between 1a and Complex B. The isomerization of 1-naphthyl-
OD by keto–enol tautomerization seems to result in deutera-
tion of the 2-position. The deuterium incorporation into the 4-
position may occur via the isomerization of complex A. Since
the OH group acts as electron-donating group for the 4-posi-
tion, an alternative route via direct C–H activation unlikely oc-
curs. On the other hand, deuteration at the 3-position may oc-
cur by direct C–H activation, as in the rhodium catalyzed
ortho-alkylation of aromatic ketones,15 since the isomerization
of A to give a complex bearing iridium at the site is impossi-
ble. The H–D exchange of 1a at the 8-position using metha-
nol-d1 appears to occur in Complex B. The exchange at the 2-,
3-, and 4-positions may proceed as in the case using styrene-
d8.
The fact that, using [RhCl(cod)]2, neither the coupling of 1a
with 2a nor the H–D exchange with styrene-d8 took place is at-
tributable to its inability to cleave the peri C–H bond. Never-
theless, in the presence of the rhodium species, the 3-position
of 1a was deuterated by methanol-d1 to some extent. In con-
nection with this, the catalytic dehydrogenation of tetralin (39)
to naphthalene (40), which proceeds via cleavege of the ben-
zylic C–H bond, was examined using [IrCl(cod)]2 and
[RhCl(cod)]2 together with PBut3 (Scheme 11).19–21 Both met-
al species could catalyze the reaction, while the rhodium spe-
cies unexpectedly showed better activity. These results indi-
cate that the rhodium catalyst may have similar ability to di-
rectly activate aromatic and benzylic C–H bonds to that of the
iridium catalyst. Thus, the origin of different behaviors be-
tween the rhodium and iridium species with respect to the peri-
interaction is not definitive at the present stage.
[RhCl(cod)]2, the 2- and 3-positions were deuterated (Entry 6).
The 2-position was deuterated significantly without any metal
species (Entry 7). These results indicate that the iridium cata-
lyst can activate the C–H bonds at the 3- and 4-positons as well
as the expected 8-position,16 whereas only the C–H bond at the
3-position is cleaved to some extent by the rhodium species. It
is noted that 2,4,6-trimethylphenol (30) was not deuterated by
treatment with methanol-d1 in the presence of the iridium cata-
lyst, suggesting that the methyl hydrogens are not attacked.
Reaction Mechanism. A plausible mechanism for the re-
action of 1 or 15 with 2 is illustrated in Scheme 10 in which
neutral ligands on iridium as well as substituents on the sub-
strate are omitted for clarity. The reaction may involve initial
coordination of 1 or 15 to a chloroiridium(Ⅰ) species to form
naphtholate or amide complex A, accompanied by liberation of
HCl. Then, oxidative addition of the aromatic C–H bond at the
8-position to the metal center occurs to give arylhydridoiridi-
um(Ⅲ) complex B. After insertion of 2 to the Ir–H bond in B
to produce complex C, reductive elimination gives complex D.
Complex A is, then, reproduced by ligand exchange with 1 or
15 accompanied by liberation of the product.
A possible role of the added base, Na2CO3, seems to be re-
moval of the initially formed HCl, as has been proposed for the
rhodium-catalyzed reaction of salicylaldehydes (Scheme 2).5
It should be noted that beneficial effects of the bulky phos-
phine, PBut3, in various catalytic reactions have recently been
reported,17,18 especially in palladium-catalyzed arylation reac-
tions using aryl halides.17 The phosphine is considered to co-
ordinate to palladium, forming a complex having a P/Pd ratio
of 1, and it promotes initial oxidative addition and final reduc-
tive elimination. Although its role in the present reaction is not
definitive, it may be reasonable to consider that the phosphine
enhances the reductive elimination of complex C to D due to
In order to discuss the substituent electronic effects, it is
worth noting those observed in the rhodium-catalyzed reaction
of salicylaldehyde with alkynes (Scheme 2).5b In the normal
aldehyde–alkyne coupling, the aldehydes having an electron-
donating group reacts faster than those having an electron-
withdrawing group. In contrast, in the competitive reaction us-
ing two different substituted salicylaldehydes, the aldehyde
having an electron-withdrawing group is consumed preferably.
Scheme 11. Reaction conditions: 39 (4 cm3), [MCl(cod)]2
(0.005 mmol), PBut3 (0.02 mmol), and molecular sieves
(MS4A, 300 mg), at 150 °C for 24 h under N2. TON =
(mol of H2 evolved)/(mol of M). The amount of H2 was es-
timated by the GLC yield of 40.
Scheme 10.

1732 Bull. Chem. Soc. Jpn., 74, No. 9 (2001)
Iridium-Catalyzed Reaction of 1-Naphthols
This could be interpreted as follows. In the competitive reac-
tion, the substrates having higher acidities coordinate to the
metal center more readily, and thus react faster. In the inde-
pendent reaction, the relative ease of the final catalytic step is
one of the most important factors determining the overall reac-
tion rate. Thus, the rate of the final step, product-substrate ex-
change, depends on the difference of acidity as well as the ster-
ic bulkiness between the coupling products and the starting
materials. With the same argument, the electronic effects ob-
served in the coupling of 1 or 15 with 2a could be explained at
least for the competitive reactions. As it happens, the final step
of the independent reactions using the substrates having an
electron-withdrawing substituent would be relatively fast.
Meanwhile, in the present reaction, the transformation of A to
B, that is oxidative addition, may also be enhanced by an elec-
tron-withdrawing substituent. Therefore, a further investiga-
tion is required to clarify the predominant factor of the substit-
uent effects.
Chart 2. NOE peak enhancement in the measurement of 1H
NMR of 3.
2.24 (s, 3H), 2.62–2.70 (m, 1H), 5.34 (dd, J = 8.3, 6.2 Hz, 1H),
7.08–7.13 (m, 2H), 7.36–7.44 (m, 2H), 7.73–7.77 (m, 2H); 13C
NMR δ 14.10, 14.23, 21.00, 21.34, 23.12, 30.60, 35.01, 119.87,
124.91, 125.08, 125.63, 127.09, 127.50, 127.72, 129.58, 135.80,
139.70, 143.34, 146.64, 169.78; MS m/z 296 (M+). Anal. Calcd
for C20H24O2: C, 81.04; H, 8.16%. Found: C, 80.83; H, 8.30%.
2-Methyl-8-[(E)-4-octen-4-yl]-1-naphthol (4): Oil;1H NMR
δ 0.87 (t, J = 7.3 Hz, 3H), 1.01 (t, J = 7.3 Hz, 3H), 1.25–1.42 (m,
2H), 1.53 (qt, J = 7.3, 7.3 Hz, 2H), 2.23–2.42 (m, 3H), 2.36 (s,
3H), 2.59–2.67 (m, 1H), 5.81 (t, J = 7.3 Hz, 1H), 6.99 (dd, J =
7.0, 1.1 Hz, 1H), 7.25 (d, J = 8.0 Hz, 1H), 7.27 (t, J = 8.0 Hz,
1H), 7.33 (d, J = 8.0 Hz, 1H), 7.67 (dd, J = 8.0, 1.1 Hz, 1H), 7.71
(s, 1H); 13C NMR δ 13.97, 14.15, 16.28, 20.92, 22.70, 30.30,
35.30, 119.69, 119.81, 121.17, 123.85, 127.03, 127.78, 129.58,
133.40, 134.30, 137.60, 143.64, 150.54; MS m/z 268 (M+). Anal.
Calcd for C19H24O: C, 85.03; H, 9.01%. Found: C, 84.98; H,
8.98%.
4-Chloro-8-[(E)-4-octen-4-yl]-1-naphthyl Acetate (Acetate
of 5): Mp 46–47 °C; 1H NMR δ 0.84 (t, J = 7.3 Hz, 3H), 1.00 (t,
J = 7.3 Hz, 3H), 1.15–1.30 (m, 2H), 1.43–1.57 (m, 2H), 2.07–
2.34 (m, 3H), 2.24 (s, 3H), 2.62–2.70 (m, 1H), 5.34 (dd, J = 8.3,
6.2 Hz, 1H), 7.02 (d, J = 8.3 Hz, 1H), 7.20 (dd, J = 7.3, 1.5 Hz,
1H), 7.51 (dd, J = 8.3, 7.3 Hz, 1H), 8.24 (dd, J = 8.3, 1.5 Hz,
1H); 13C NMR δ 14.11, 14.24, 20.98, 21.33, 23.11, 30.62, 35.08,
118.15, 119.74, 124.15, 124.17, 125.53, 125.98, 126.82, 128.03,
130.18, 130.56, 143.08, 145.70, 169.61; MS m/z 330, 332 (M+).
Anal. Calcd for C20H23ClO2: C, 72.61; H, 7.01. Cl, 10.72%.
Found: C, 72.38; H, 6.99; Cl, 10.52%.
Experimental
1H and 13C NMR spectra were recorded at 400 MHz and 100
MHz, respectively, for CDCl3 solutions. MS data were obtained
by EI. GC analysis was carried out using a silicone OV-17 glass
column (i.d. 2.6 mm × 1.5 m). 1-Naphthols 1e and 1f were pre-
pared by the reactions of 5-amino-1-naphthol with trifluoroacetic
anhydride in ether and of 1,5-dihydroxynaphthalene with dimeth-
yl sulfate in the presence of aq KOH, respectively. Sulfonamides
14a–e were prepared by the reactions of 1-naphthylamine hydro-
chloride with the corresponding sulfonyl chlorides in pyridine.
Other starting materials were commercially available. The follow-
ing experimental details given below may be regarded as typical in
methodology and scale.
Reaction of 1-Naphthol (1a) with 4-Octyne (2a): A mix-
ture of 1a (288 mg, 2 mmol), 2a (220 mg, 2 mmol), [IrCl(cod)]2 (7
mg, 0.01 mmol), PBut3 (6 mg, 0.03 mmol), Na2CO3 (11 mg, 0.1
mmol), and 1-methylnaphthalene (ca. 100 mg, internal standard)
in refluxing toluene (5 cm3) at a bath temperature of 135 °C was
stirred under nitrogen for 2 h. After cooling, the reaction mixture
was extracted with diethyl ether, and dried over sodium sulfate.
GC and GC-MS analyses confirmed the formation of 8-[(E)-4-
octen-4-yl]-1-naphthol (3) in 83% yield. The product (303 mg,
60%) was also isolated by column chromatography on silica gel
using hexane–ethyl acetate (99.7:0.3, v/v) as eluent. Compound 3
was an oil: 1H NMR δ 0.88 (t, J = 7.3 Hz, 3H, Hc), 1.01 (t, J = 7.3
Hz, 3H, Hcꢀ), 1.28–1.42 (m, 2H, Hb), 1.53 (qt, J = 7.3, 7.3 Hz, 2H,
Hbꢀ), 2.22–2.36 (m, 2H, Haꢀ), 2.37–2.45 (m, 1H, Ha), 2.57–2.65 (m,
1H, Ha), 5.80 (t, J = 7.3 Hz, 1H, Hvinyl), 6.93 (dd, J = 7.3, 1.2 Hz,
1H, H2), 7.03 (d, J = 7.1 Hz, 1H, H7), 7.32–7.36 (m, 2H, H3 and
H5), 7.40 (dd, J = 8.3, 1.2 Hz, 1H, H4), 7.60 (s, 1H, OH), 7.72 (d,
J = 8.3, 1.2 Hz, 1H, H5); 13C NMR δ 14.11, 14.33, 21.13, 22.81,
30.41, 35.44, 111.03, 120.48, 121.30, 124.71, 126.40, 126.77,
127.71, 133.25, 135.57, 137.98, 143.23, 153.40; MS m/z 254
(M+). The assignment of the 1H NMR peaks was made by means
of H–H COSY. NOE peak enhancements for determining the con-
figuration are shown in Chart 2.
4-Methoxy-8-[(E)-4-octen-4-yl]-1-naphthyl Acetate (Ace-
tate of 6): Oil; 1H NMR δ 0.83 (t, J = 7.3 Hz, 3H), 1.00 (t, J =
7.3 Hz, 3H), 1.14–1.34 (m, 2H), 1.42–1.59 (m, 2H), 2.05–2.34 (m,
3H), 2.22 (s, 3H), 2.40–2.69 (m, 1H), 3.99 (s, 3H), 5.33 (dd, J =
8.3, 6.2 Hz, 1H), 6.77 (d, J = 8.3 Hz, 1H), 7.00 (d, J = 8.3 Hz,
1H), 7.15 (dd, J = 6.8, 1.5 Hz, 1H), 7.38 (dd, J = 8.3, 6.8 Hz,
1H), 8.23 (dd, J = 8.3, 1.5 Hz, 1H); 13C NMR δ 14.12, 14.25,
20.99, 21.35, 23.15, 30.63, 35.06, 55.74, 102.93, 119.24, 121.44,
125.02, 125.43, 127.12, 127.61, 130.24, 139.39, 139.94, 143.44,
153.84, 170.29.
HRMS m/z (M+), Calcd for C21H26O3:
326.1882%. Found: 326.1872%.
8-[(E)-4-Octen-4-yl]-5-trifluoroacetylamino-1-naphthyl Ace-
1
tate (Acetate of 7): Oil; H NMR δ 0.83 (t, J = 7.3 Hz, 3H),
1.01 (t, J = 7.3 Hz, 3H), 1.15–1.57 (m, 4H), 2.08–2.34 (m, 3H),
2.25 (s, 3H), 2.62–2.70 (m, 1H), 5.32 (dd, J = 8.3, 6.2 Hz, 1H),
7.10–7.14 (m, 2H), 7.46 (t, J = 8.3 Hz, 1H), 7.59–7.62 (m, 2H),
8.27 (s, 1H); 13C NMR δ 14.10, 14.21, 20.98, 21.32, 23.10, 30.60,
35.00, 116.11 (q, JC-F = 271 Hz), 119.36, 120.75, 122.31, 125.59,
126.32, 128.18, 128.43, 129.05, 129.56, 139.83, 143.02, 147.27,
155.81 (q, JC-F = 37 Hz), 169.88; MS m/z 407 (M+). Anal. Calcd
for C22H24F3NO3: C, 64.86; H, 5.94; N, 3.44%. Found: C, 64.64;
H, 5.91; N, 3.45%.
In another run using the same conditions, the crude product was
acetylated with Ac2O (1 cm3) in pyridine (5 cm3) at room tempera-
ture for 16 h, and then purified by column chromatography to give
the acetate of 3 (368 mg, 59%). The acetate was an oil: 1H NMR δ
0.84 (t, J = 7.3 Hz, 3H), 1.00 (t, J = 7.3 Hz, 3H), 1.16–1.34 (m,
2H), 1.43–1.57 (m, 2H), 2.08–2.16 (m, 1H), 2.22–2.34 (m, 3H),

Y. Nishinaka et al.
Bull. Chem. Soc. Jpn., 74, No. 9 (2001) 1733
5-Methoxy-8-[(E)-4-octen-4-yl]-1-naphthyl Acetate (Ace-
tate of 8): Oil; 1H NMR δ 0.84 (t, J = 7.3 Hz, 3H), 1.00 (t, J =
7.3 Hz, 3H), 1.15–1.35 (m, 2H), 1.43–1.56 (m, 2H), 2.05–2.41 (m,
3H), 2.23 (s, 3H), 2.58–2.67 (m, 1H), 3.97 (s, 3H), 5.31 (dd, J =
8.3, 6.2 Hz, 1H), 6.73 (d, J = 7.8 Hz, 1H), 7.03 (d, J = 7.8 Hz,
1H), 7.12 (dd, J = 7.3, 1.5 Hz, 1H), 7.43 (dd, J = 8.3, 7.3 Hz,
1H), 8.23 (dd, J = 8.3, 1.5 Hz, 1H); 13C NMR δ 14.12, 14.25,
20.98, 21.37, 23.18, 30.63, 35.12, 55.55, 103.58, 120.50, 120.88,
124.48, 125.67, 127.55, 127.72, 129.39, 131.92, 143.37, 146.48,
154.46, 169.79; MS m/z 326 (M+). Anal. Calcd for C21H26O3: C,
77.27; H, 8.03%. Found: C, 77.07; H, 8.09%.
MS m/z 427, 429 (M+). Anal. Calcd for C24H27ClNO2S: C, 67.35;
H, 6.12; N, 3.27%. Found: C, 67.12; H, 6.09; N, 3.25%.
1-Benzenesulfonamido-8-[(E)-4-octen-4-yl]naphthalene
1
(17): Oil; H NMR δ 0.83 (t, J = 7.3 Hz, 3H), 1.06 (t, J = 7.3
Hz, 3H), 1.16–1.35 (m, 2H), 1.53–1.73 (m, 2H), 2.05–2.09 (m,
1H), 2.20–2.33 (m, 1H), 2.39–2.48 (m, 1H), 2.72–2.80 (m, 1H),
5.76 (t, J = 7.3 Hz, 1H), 7.03 (d, J = 7.3 Hz, 1H), 7.28–7.40 (m,
4H), 7.45–7.54 (m, 3H), 7.66 (d, J = 8.3 Hz, 1H), 7.81 (d, J = 7.3
Hz, 2H), 9.06 (s, 1H); 13C NMR δ 14.04, 14.15, 20.85, 22.60,
30.39, 35.50, 114.79, 121.98, 124.76, 125.11, 125.42, 127.20,
128.30, 128.84, 129.01, 132.84, 133.34, 133.87, 135.34, 138.58,
139.74, 143.32; MS m/z 393 (M+). Anal. Calcd for C24H27NO2S:
C, 73.25; H, 6.92; N, 3.56%. Found: C, 73.35; H, 6.99; N, 3.53%.
1-(4-Methylbenzenesulfonamido)-8-[(E)-4-octen-4-yl]naph-
1
8-[(E)-5-Decen-5-yl]-1-naphthol (9): Oil; H NMR δ 0.83
(t, J = 7.3 Hz, 3H), 0.96 (t, J = 7.3 Hz, 3H), 1.24–1.53 (m, 8H),
2.22–2.44 (m, 3H), 2.60–2.69 (m, 1H), 5.78 (t, J = 7.3 Hz, 1H),
6.93 (dd, J = 7.3, 1.0 Hz, 1H), 7.04 (dd, J = 7.3, 1.0 Hz, 1H),
7.33–7.37 (m, 2H), 7.41 (d, J = 8.3, 1.0 Hz, 1H), 7.61 (s, 1H),
7.73 (dd, J = 8.3, 1.0 Hz, 1H); 13C NMR δ 13.85, 13.94, 22.50,
22.84, 27.92, 29.89, 31.59, 33.04, 111.13, 120.62, 121.43, 124.87,
126.54, 126.91, 127.84, 133.43, 135.75, 138.21, 143.38, 153.63;
MS m/z 282 (M+). Anal. Calcd for C20H26O: C, 85.06; H, 9.28%.
Found: C, 84.86; H, 8.79%.
1
thalene (18): Mp 99–100 °C; H NMR δ 0.83 (t, J = 7.3 Hz,
3H), 1.06 (t, J = 7.3 Hz, 3H), 1.16–1.37 (m, 2H), 1.54–1.73 (m,
2H), 2.05–2.14 (m, 1H), 2.23–2.52 (m, 2H), 2.33 (s, 3H), 2.73–
2.82 (m, 1H), 5.77 (t, J = 7.3 Hz, 1H), 7.03 (d, J = 6.8 Hz, 1H),
7.18 (d, J = 8.3 Hz, 2H), 7.28–7.40 (m, 2H), 7.51 (t, J = 6.8 Hz,
2H), 7.66 (d, J = 8.3 Hz, 1H), 7.71 (d, J = 8.3 Hz, 2H), 9.07 (s,
1H); 13C NMR δ 14.05, 14.15, 20.85, 21.45, 22.61, 30.39, 35.53,
114.49, 121.91, 124.55, 125.06, 125.44, 127.32, 128.30, 128.97,
129.47, 133.33, 134.03, 135.36, 136.80, 138.65, 143.36, 143.71;
MS m/z 407 (M+). Anal. Calcd for C25H29NO2S: C, 73.67; H,
7.17; N, 3.44%. Found: C,73.58; H, 7.15; N, 3.41%.
8-[(E)-2,9-Dimethyl-5-decen-5-yl]-1-naphthol (10): Oil; 1H
NMR δ 0.82 (d, J = 6.8 Hz, 3H), 0.84 (d, J = 6.4 Hz, 3H), 0.95
(d, J = 6.4 Hz, 6H), 1.25–1.34 (m, 2H), 1.35–1.41 (m, 2H), 1.44–
1.70 (m, 2H), 2.21–2.42 (m, 3H), 2.63–2.70 (m, 1H), 5.76 (t, J =
7.3 Hz, 1H), 6.93 (dd, J = 7.3, 1.5 Hz, 1H), 7.03 (dd, J = 7,3, 1.5
Hz, 1H), 7.33–7.37 (m, 2H) 7.41 (dd, J = 7.3, 1.5 Hz, 1H) 7.60 (s,
1H), 7.73 (dd, J = 8.3, 1.0 Hz, 1H); 13C NMR δ 22.38, 22.43,
22.53, 26.10, 27.82, 28.23, 31.24, 36.84, 38.54, 111.15, 120.62,
121.41, 124.87, 126.54, 126.89, 127.84, 133.35, 135.74, 138.25,
143.48, 153.62; MS m/z 310 (M+). Anal. Calcd for C22H30O: C,
85.11; H, 9.74%. Found: C, 84.67; H, 9.72%.
8-[(E)-2-Hepten-2-yl]-1-naphthol (11) and 8-[(E)-2-Hepten-
3-yl]-1-naphthol (12): Oil (11/12 = 62:38); 1H NMR δ 0.84 (t,
J = 7.3 Hz, 3H × 0.38, 12), 0.96 (t, J = 7.3 Hz, 3H × 0.62, 11),
1.25–1.52 (m, 8H), 1.90 (d, J = 6.8 Hz, 3H × 0.38, 12), 2.12 (s,
3H × 0.62, 11), 2.25–2.35 (m, 2H × 0.62, 11), 2.37–2.45 (m, 1H
× 0.38, 12), 2.58–2.70 (m, 1H × 0.38, 12), 5.77 (t, J = 7.3 Hz,
1H × 0.62, 11), 5.85 (q, J = 6.8 Hz, 1H × 0.38, 12), 6.92–6.95
(m, 1H), 7.02–7.07 (m, 1H), 7.32–7.43 (m, 3H), 7.54 (s, 1H ×
0.38, 12), 7.60 (s, 1H × 0.62, 11), 7.71–7.74 (m, 1H); MS m/z 240
(M+). Anal. Calcd for C17H20O: C, 84.96; H, 8.39%. Found: C,
84.93; H, 8.50%.
8-[(E)-1-Phenyl-1-propen-2-yl]-1-naphthyl Acetate (Ace-
tate of 13) and 8-[(E)-1-Phenyl-1-propen-1-yl]-1-naphthyl Ac-
etate (Acetate of 14): Oil (13/14 = 79:21); 1H NMR δ 1.94 (s,
3H × 0.79, 13), 2.01 (d, J = 7.3 Hz, 3H × 0.21, 14), 2.17 (s, 3H
× 0.21, 14), 2.34 (s, 3H × 0.79, 13), 5.71 (q, J = 7.3 Hz, 1H ×
0.21, 14), 6.40 (s, 1H × 0.79, 13), 7.08 (dd, J = 7.3, 1.1 Hz, 1H ×
0.21, 14), 7.13 (dd, J = 7.3, 1.1 Hz, 1H × 0.79, 13), 7.19–7.31
(m, 3H), 7.37–7.75 (m, 5H), 7.77–7.83 (m, 2H); MS m/z 302
(M+). Anal. Calcd for C21H18O2: C, 83.42; H, 6.00%. Found: C,
84.18; H, 5.89%.
1-(4-Methoxybenzenesulfonamido)-8-[(E)-4-octen-4-yl]-
1
naphthalene (19): Oil; H NMR δ 0.84 (t, J = 7.3 Hz, 3H),
1.07 (t, J = 7.3 Hz, 3H), 1.17–1.35 (m, 2H), 1.54–1.72 (m, 2H),
2.06–2.13 (m, 1H), 2.20–2.32 (m, 1H), 2.40–2.50 (m, 1H), 2.73–
2.81 (m, 1H), 3.78 (s, 3H), 5.77 (t, J = 7.3 Hz, 1H), 6.84 (d, J =
8.8 Hz, 2H), 7.03 (dd, J = 6.9, 1.0 Hz, 1H), 7.29–7.40 (m, 2H),
7.50–7.54 (m, 2H), 7.66 (d, J = 8.3 Hz, 1H), 7.75 (d, J = 8.3 Hz,
2H), 9.03 (s, 1H); 13C NMR δ 14.06, 14.16, 20.85, 22.62, 30.41,
35.53, 55.51, 114.01, 114.48, 121.92, 124.52, 125.07, 125.44,
128.30, 128.97, 129.47, 131.30, 133.34, 134.09, 135.36, 138.65,
143.31, 163.02; MS m/z 423 (M+). Anal. Calcd for C25H29NO3S:
C, 70.89; H, 6.90; N, 3.31%. Found: C, 70.80; H, 6.98; N, 3.22%.
1-(4-Chlorobenzenesulfonamido)-8-[(E)-5-decen-5-yl]naph-
thalene (20): Oil; 1H NMR δ 0.81 (t, J = 6.8 Hz, 3H), 0.84 (t, J
= 6.8 Hz, 3H), 1.13–1.34 (m, 4H), 1.43–1.66 (m, 4H), 1.99–2.08
(m, 1H), 2.26–2.48 (m, 2H), 2.76–2.85 (m, 1H), 5.73 (t, J = 7.3
Hz, 1H), 7.04 (d, J = 7.3 Hz, 1H), 7.30–7.38 (m, 4H), 7.53 (t, J =
8.3 Hz, 2H), 7.68–7.74 (m, 3H), 9.06 (s, 1H); 13C NMR δ 13.86,
14.01, 22.67, 22.72, 28.02, 29.85, 31.56, 33.28, 114.94, 121.90,
125.12, 125.25, 125.39, 128.38, 128.65, 129.14, 129.17, 129.25,
133.48, 133.56, 135.38, 138.49, 139.41, 143.26; MS m/z 455, 457
(M+). Anal. Calcd for C26H30ClNO2S: C, 68.48; H, 6.63; N
3.07%. Found: C, 68.44; H, 6.60; N, 3.00%.
1-(4-Chlorobenzenesulfonamido)-8-[(E)-2,9-dimethyl-5-de-
cen-5-yl]naphthalene (21): Oil; 1H NMR δ 0.76 (d, J = 6.5 Hz,
3H), 0.84 (d, J = 6.5 Hz, 3H), 0.99 (d, J = 6.5 Hz, 6H), 1.09–1.26
(m, 2H), 1.37–1.57 (m, 3H), 1.65–1.75 (m, 1H), 1.95–2.03 (m,
1H), 2.18–2.43 (m, 2H), 2.78–2.85 (m, 1H), 5.70 (t, J = 7.3 Hz,
1H), 7.03 (dd, J = 6.8, 1.0 Hz, 1H), 7.30–7.35 (m, 4H), 7.53–7.55
(m, 2H), 7.67–7.74 (m, 3H), 9.05 (s, 1H); 13C NMR δ 14 .10,
22.36, 22.42, 22.48, 22.58, 22.64, 26.13, 27.95, 28.14, 31.49,
31.57, 36.83, 38.52, 114.97, 122.01, 125.12, 125.39, 128.38,
128.63, 129.14, 129.18, 133.39, 133.55, 135.39, 138.24, 138.51,
139.40, 143.37; MS m/z 483, 485 (M+). Anal. Calcd for
C28H34ClNO2S: C, 69.47; H, 7.08; N, 2.89%. Found: C, 69.70; H,
7.20; N, 2.79%.
1-(4-Chlorobenzenesulfonamido)-8-[(E)-4-octen-4-yl]naph-
1
thalene (16): Mp 83–85 °C; H NMR δ 0.83 (t, J = 7.3 Hz,
3H), 1.06 (t, J = 7.3 Hz, 3H), 1.13–1.37 (m, 2H), 1.55–1.73 (m,
2H), 2.02–2.09 (m, 1H), 2.22–2.32 (m, 1H), 2.38–2.47 (m, 1H),
2.71–2.78 (m, 1H), 5.83 (t, J = 7.3 Hz, 1H), 7.04 (d, J = 7.3 Hz,
1H), 7.30–7.36 (m, 4H), 7.51–7.55 (m, 2H), 7.67–7.74 (m, 3H),
9.07 (s, 1H); 13C NMR δ 14.04, 14.15, 20.87, 22.62, 30.40, 35.51,
114.95, 122.00, 125.12, 125.23, 125.38, 128.38, 128.64, 129.14,
129.14, 133.46, 133.55, 135.37, 138.18, 138.44, 139.40, 143.24;
1-(4-Chlorobenzenesulfonamido)-8-[(E)-2-hepten-2-yl]-

1734 Bull. Chem. Soc. Jpn., 74, No. 9 (2001)
Iridium-Catalyzed Reaction of 1-Naphthols
naphthalene (22) and 1-(4-Chlorobenzenesulfonamido)-8-[(E)-
2-hepten-3-yl]naphthalene (23): Oil(22/23=57:43);1H NMR
δ 0.82 (t, J = 6.9 Hz, 3H × 0.43, 23), 0.99 (t, J = 6.9 Hz, 3H ×
0.57, 22), 1.15–1.65 (m, 4H), 1.96 (d, J = 6.9 Hz, 3H × 0.43, 23),
2.05 (s, 3H × 0.57, 22), 2.28–2.84 (m, 2H), 5.67 (t, J = 7.3 Hz,
1H × 0.57, 22), 5.77 (q, J = 6.9 Hz, 1H × 0.43, 23), 7.03 (dd, J
= 7.3, 1.1 Hz, 1H × 0.43, 23), 7.09 (dd, J = 6.9, 1.1 Hz, 1H ×
0.57, 22), 7.30–7.41 (m, 4H), 7.50–7.57 (m, 2H), 7.68–7.73 (m,
3H), 9.01 (s, 1H × 0.57, 22), 9.06 (s, 1H × 0.43, 23); MS m/z
413, 415 (M+). Anal. Calcd for C23H24ClO2NS: C, 66.73; H, 5.84;
N, 3.38%. Found: C, 66.55; H, 5.85; N, 3.38%.
6H), 7.68 (d, J = 7.8 Hz, 1H × 0.15, 38), 7.77 (d, J = 7.8, 1H ×
0.85, 37), 11.85 (s, 1H × 0.85, 37), 12.03 (s, 1H × 0.15, 38); MS
m/z 238 (M+). Anal. Calcd for C16H14O2: C, 80.65; H, 5.92%.
Found: C, 80.49; H, 5.96%.
References
1
For reviews, see: a) G. R. Newkome, W. E. Puckett, V. K.
Gupta, and G. E. Kiefer, Chem. Rev., 86, 451 (1986). b) A. D.
Ryabov, Chem. Rev., 90, 403 (1990). c) A. E. Shilov and G. B.
Shul’pin, Chem. Rev., 97, 2879 (1997).
1-Methanesulfonamido-8-[(E)-4-octen-4-yl]naphthalene
(24): Oil; H NMR δ 0.87 (t, J = 7.3 Hz, 3H), 1.03 (t, J = 7.3
2
F. Kakiuchi and S. Murai, in “Activation of Unreactive
1
Bonds and Organic Synthesis,” ed by S. Murai, Springer, Berlin
(1999), p. 47.
Hz, 3H), 1.22–1.44 (m, 2H), 1.48–1.69 (m, 2H), 2.12–2.30 (m,
2H), 2.34–2.44 (m, 1H), 2.71–2.81 (m, 1H), 2.97 (s, 3H), 5.81 (t, J
= 7.3 Hz, 1H), 7.03 (dd, J = 6.8, 1.0 Hz, 1H), 7.38–7.44 (m, 2H),
7.61–7.65 (m, 2H), 7.75 (d, J = 8.3 Hz, 1H), 8.80 (s, 1H); 13C
NMR δ 14.08, 14.12, 20.92, 22.53, 30.39, 35.43, 38.99, 114.59,
121.99, 125.02, 125.39, 125.70, 128.48, 129.23, 133.60, 134.12,
135.59, 138.68, 143.01; MS m/z 331, 333 (M+). Anal. Calcd for
C19H25NO2S: C, 68.85; H, 7.60; N, 4.23%. Found: C, 68.82; H,
7.58; N, 4.08%.
3
For reviews, see: a) S. Murai, N. Chatani, and F. Kakiuchi,
Pure Appl. Chem., 69, 589 (1997). b) G. Dyker, Angew. Chem.,
Int. Ed., 38, 1698 (1999). c) Y. Guari, S. Sabo-Etienne, B.
Chaudret, Eur. J. Inorg. Chem., 1999, 1047. d) C.-H. Jun, J.-B.
Hong, and D.-Y. Lee, Synlett, 1999, 1.
4
T. Satoh, T. Itaya, M. Miura, and M. Nomura, Chem. Lett.,
1996, 823.
5
a) K. Kokubo, K. Matsumasa, M. Miura, and M. Nomura,
4-Hydroxy-5-[(E)-4-octen-4-yl]coumarin (26): Mp 152–
153 °C; 1H NMR δ 0.91 (t, J = 7.3 Hz, 3H), 1.00 (t, J = 7.3 Hz,
3H), 1.23–1.43 (m, 2H), 1.47–1.56 (m, 2H), 2.20–2.30 (m, 2H),
2.32–2.57 (m, 2H), 5.73 (t, J = 7.3 Hz, 1H), 5.81 (s, 1H), 6.95
(dd, J = 7.3, 1.0 Hz, 1H), 7.30 (dd, J = 7.8, 1.0 Hz, 1H), 7.48 (t, J
= 7.8 Hz, 1H), 8.77 (s, 1H); 13C NMR δ 13.84, 14.13, 21.24,
22.46, 30.24, 35.14, 94.24, 112.46,116.50, 125.90, 131.37,
134.78, 140.52, 140.67, 154.55, 163.16, 166.09; MS m/z 272
(M+). Anal. Calcd for C17H20O3: C, 74.97; H, 7.40%. Found: C,
74.85; H, 7.34%.
J. Org. Chem., 62, 4564 (1997). b) K. Kokubo, K. Matsumasa, Y.
Nishinaka, M. Miura, and M. Nomura, Bull. Chem. Soc. Jpn., 72,
303 (1999).
6
a) T. Satoh, Y. Kawamura, M. Miura, and M. Nomura, An-
gew. Chem., Int. Ed. Engl., 36, 1740 (1997). b) T. Satoh, J. Inoh,
Y. Kawamura, Y. Kawamura, M. Miura, and M. Nomura, Bull.
Chem. Soc. Jpn., 71, 2239 (1998). c) Y. Kawamura, T. Satoh, M.
Miura, and M. Nomura, Chem. Lett., 1999, 961.
7
M. Miura, T. Tsuda, T. Satoh, and M. Nomura, Chem. Lett.,
1997, 1103.
4-Hydroxy-1-methyl-5-[(E)-4-octen-4-yl]-2(1H)-quinolone
(28): Mp 189–190 °C; 1H NMR δ 0.89 (t, J = 7.3 Hz, 3H), 0.97
(t, J = 7.3 Hz, 3H), 1.20–1.43 (m, 2H), 1.45–1.56 (m, 2H), 2.15–
2.37 (m, 3H), 2.54–2.62 (m, 1H), 3.46 (s, 3H), 5.58 (t, J = 7.3 Hz,
1H), 6.13 (s, 1H), 6.89 (d, J = 7.3 Hz, 1H), 7.23 (d, J = 8.3 Hz,
1H), 7.48 (t, J = 8.3 Hz, 1H), 9.93 (s, 1H); 13C NMR δ 13.88,
14.15, 21.28, 22.60, 29.43, 30.23, 35.34, 99.86, 113.66, 113.81,
124.50, 129.84, 131.72, 140.89, 141.99, 142.45, 162.93, 164.01;
MS m/z 285 (M+). Anal. Calcd for C18H23NO2: C, 75.76; H, 8.12;
N, 4.91%. Found: C, 75.58; H, 8.10; N, 4.94%.
8
Related stoichiometric C–H bond activation reactions in-
volving phenolic function as directing group: a) I. P. Rothwell,
Acc. Chem. Res., 21, 153 (1988). b) H. E. Bryndza and W. Tam,
Chem. Rev., 88, 1163 (1988). c) T. Hascall, V. J. Murphy, and G.
Parkin, Organometallics, 15, 3910 (1996). d) H.-F. Klein, A.
Bickelhaupt, M. Lemke, H. Sun, A. Brand, T. Jung, C. Röhr, U.
Flörke, and H.-J. Haupt, Organometallics, 16, 668 (1997). e) M.
Hirano, N. Kurata, T. Marumo, and S. Komiya, Organometallics,
17, 501 (1998).
9
a) A. J. Kirby and J. M. Percy, Tetrahedron, 44, 6911
(E)-1-(2-Hydroxyphenyl)-2-propyl-2-hexcen-1-one (34):
Oil; the NMR data were the same those reported previously.5b
(E)-1-(2-Hydroxyphenyl)-2-methyl-2-hepten-1-one (35) and
(E)-1-(2-Hydroxyphenyl)-2-butyl-2-buten-1-one (36): Oil
(35/36 = 82:18); 1H NMR δ 0.90 (t, J = 6.8 Hz, 3H × 0.18, 36),
0.94 (t, J = 6.8 Hz, 3H × 0.82, 35), 1.32–1.50 (m, 4H), 1.89 (d, J
= 7.3 Hz, 3H × 0.18, 36), 1.97 (s, 3H × 0.82, 35), 2.29 (dt, J =
7.3,7.3 Hz, 2H × 0.82, 35), 2.79 (t, J = 7.3 Hz, 2H × 0.18, 36),
6.06 (q, J = 7.3 Hz, 1H × 0.18, 36), 6.09 (t, J = 7.3 Hz, 1H ×
0.82, 35), 6.83–6.88 (m, 1H), 6.98–7.01 (m, 1H), 7.43–7.47 (m,
1H), 7.62–7.66 (m, 1H), 11.83 (s, 1H × 0.82, 35), 11.93 (s, 1H ×
0.18, 36); MS m/z 218 (M+). Anal. Calcd for C14H18O2: C, 77.03;
H, 8.31%. Found: C, 76.92; H, 8.40%.
(E)-1-(2-Hydroxyphenyl)-2-methyl-3-phenyl-2-propen-1-
one (37) and 1-(2-(E)-Hydroxyphenyl)-2-phenyl-2-buten-1-one
(38): Oil (37/38 = 85:15); 1H NMR δ 1.93 (d, J = 7.3 Hz, 3H
× 0.15, 38), 2.27 (s, 3H × 0.85, 37), 6.34 (q, J = 7.3 Hz, 1H ×
0.15, 38), 6.80 (t, J = 7.3 Hz, 1H × 0.15, 38), 6.89 (t, J = 7.3 Hz,
1H × 0.85, 37), 6.96 (s, 1H × 0.85, 37), 6.98 (d, J = 7.3 Hz, 1H
× 0.15, 38), 7.04 (d, J = 8.3 Hz, 1H × 0.85, 37), 7.30–7.51 (m,
(1988). b) D. G. Batt, D. G. Jones, and S. L. Greca, J. Org. Chem.,
56, 6704 (1991).
10 Preliminary communication: T. Satoh, Y. Nishinaka, M.
Miura, and M. Nomura, Chem. Lett., 1999, 615.
11 “Comprehensive Organic Chemistry,” ed by D. N. Jones,
Pergamon Press, Oxford, (1979), Vol. 3, p. 345.
12 M. Miura, T. Tsuda, T. Satoh, S. Pivsa-Art, and M.
Nomura, J. Org. Chem., 63, 5211 (1998).
13 Y. Kametani, T. Satoh, M. Miura, and M. Nomura, Tetrahe-
dron Lett., 41, 2655 (2000).
14 a) F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M.
Sonoda, N. Chatani, and S. Murai, Bull. Chem. Soc. Jpn., 68, 62
(1995). b) M. Sonoda, F. Kakiuchi, A. Kamatani, N. Chatani, and
S. Murai, Bull. Chem. Soc. Jpn., 70, 3117 (1997).
15 C. P. Lenges and M. Brookhart, J. Am. Chem. Soc., 121,
6616 (1999).
16 Ir-catalyzed direct olefin arylation: T. Matsumoto, D. J.
Taube, R. A. Periana, H. Taube, and H. Yoshida, J. Am. Chem.
Soc., 122, 7414 (2000).
17 Use of PBut3 in palladium-catalyzed reactions of aryl ha-

Y. Nishinaka et al.
Bull. Chem. Soc. Jpn., 74, No. 9 (2001) 1735
lides: a) T. Yamamoto, M. Nishiyama, and Y. Koie, Tetrahedron
Lett., 39, 2367 (1998). b) G. Dyker, J. Heiermann, M. Miura, J.-I.
Inoh, S. Pivsa-Art, T. Satoh, and M. Nomura, Chem. Eur. J., 6,
3426 (2000). c) A. F. Littke, C. Dai, and G. C. Fu., J. Am. Chem.
Soc., 122, 4020 (2000). d) G. Mann, C. Incarvito, A. L.
Rheingold, and J. F. Hartwig, J. Am. Chem. Soc., 121, 3224
(1999), and references cited therein.
(TON = 20). In the absence of MS4A, considerable amounts of
α-tetralol and α-tetralone were produced.
20 Ir-catalyzed thermal dehydrogenation of alkanes and alkyl-
benzenes: a) T. Aoki and R. H. Crabtree, Organometallics, 12, 294
(1993). b) M. Gupta, W. C. Kaska, and C. M. Jensen, Chem.
Commun., 1997, 461. c) F. Liu and A. S. Goldman, Chem. Com-
mun., 1999, 655.
21 Rh-catalyzed thermal dehydrogenation of alkanes: T. Fujii,
Y. Higashino, and Y. Saito, J. Chem. Soc., Dalton Trans., 1993,
517.
18 Rh/PBut3-catalyzed reaction of arylbronic acids with alde-
hydes: M. Ueda and N. Miyaura, J. Org. Chem., 65, 4450 (2000).
19 The reaction using [IrCl(cod)]2–PPh3 was relatively slow