Rhodium-catalyzed arylative cyclization of alkynones induced by addition of arylboronic acids

Article abstract of DOI:10.1016/j.tet.2007.03.025

Alkynones react with arylboronic acids in the presence of a rhodium(I) catalyst to afford four- and five-membered-ring cyclic alcohols equipped with a tetrasubstituted exocyclic olefin. The cyclic allylic alcohol skeleton is constructed by the carbon-carb

Full text of DOI:10.1016/j.tet.2007.03.025

Tetrahedron 63 (2007) 6131–6140
Rhodium-catalyzed arylative cyclization of alkynones
induced by addition of arylboronic acids
*
Tomoya Miura, Masahiko Shimada and Masahiro Murakami
Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan
Received 15 January 2007; revised 1 March 2007; accepted 2 March 2007
Available online 12 March 2007
Abstract—Alkynones react with arylboronic acids in the presence of a rhodium(I) catalyst to afford four- and five-membered-ring cyclic
alcohols equipped with a tetrasubstituted exocyclic olefin. The cyclic allylic alcohol skeleton is constructed by the carbon–carbon bond for-
mation between the carbonyl group and an alkenylrhodium(I) intermediate formed by the regioselective addition of an arylrhodium(I) species
across the carbon–carbon triple bond.
Ó 2007 Elsevier Ltd. All rights reserved.
1. Introduction
to give arylative cyclization product (Eq. 1).5a Like carbon–
carbon double and triple bonds, the carbonyl groups of
aldehydes and ketones can also accept an organorhodium(I)
species to form a carbon–carbon bond.6 We envisaged that
an analogous sequential addition/cyclization reaction would
be feasible with an alkynone, if a carbon–carbon triple bond
and a carbonyl group are appropriately arranged in the
molecule (Eq. 2). In this paper, we wish to describe our study
on the rhodium-catalyzed reaction of alkynones with aryl-
boronic acids, which has led to the development of a new
acyl 1,3-migration reaction and a two-carbon-atom ring-
expansion reaction.7
Transition-metal-catalyzed cascade reactions involving
multiple carbometallation steps serve as a powerful method
for the preparation of complex cyclic molecules in an atom-
economical manner.1 A molecule containing two different
unsaturated functionalities that can act as an acceptor of an
organometallic species is particularly an attractive substrate
for such cascade reactions. The initial intermolecular carbo-
metallation onto the more reactive unsaturated functionality
of the two results in the incorporation of a reactive carbon–
metal linkage in the substrate molecule. The newly
generated carbon–metal bond then adds to the secondary
functionality in an intramolecular way to construct a carbo-
cyclic skeleton. Recently, rhodium(I)-catalyzed cascade
reactions2 have emerged as a complement to the well-
studied palladium-catalyzed cascade sequences.3 High func-
tional group compatibilities and stereoselectivities have
been observed in a number of the rhodium-catalyzed reac-
tions. For the rhodium(I)-catalyzed cascade reactions to
start, an alkyne moiety can provide a convenient entry point
for incorporation of an active Csp2–Rh linkage by way of
intermolecular carborhodation.4 The resultant alkenylrho-
dium(I) species exhibits an enhanced reactivity to the second
unsaturated functionality in the molecule than in an inter-
molecular case.5 For example, when 1,6-enynes were treated
with arylboronic acids in the presence of a rhodium(I) cata-
lyst, an alkenylrhodium(I) intermediate formed by the regio-
selective addition of an arylrhodium(I) species across the
carbon–carbon triple bond subsequently underwent an intra-
molecular carborhodation to the carbon–carbon double bond
R
C
R
C
Rh(I)
Rh(I)–Ar
Rh(I)–Ar
Ar
Ar
C
C
C R
C
C
C
C
C
ð1Þ
ð2Þ
Rh(I)
C
C
R
C
Rh(I)
R
C
Ar
Ar
C
C
C R
O
C
C
C
C
Rh(I)
O
O
2. Results and discussion
2.1. Arylative cyclization of alkynones
We took 5-alkyn-1-ones 1 having a three-carbon tether be-
tween the carbon–carbon triple bond and the ketonic carbon-
yl group as the model substrate and examined the reaction
with phenylboronic acid (2a). As for a rhodium catalyst,
Keywords: Rhodium; Boron; Addition; Cyclization; Alkynone.
* Corresponding author. Tel.: +81 75 383 2747; fax: +81 75 383 2748;
e-mail: murakami@sbchem.kyoto-u.ac.jp
0040–4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.03.025

6132
T. Miura et al. / Tetrahedron 63 (2007) 6131–6140
we employed hydroxo(diolefin)rhodium(I) complexes,8
which successfully catalyzed the cascade reaction of 1,6-
enynes with arylboronic acids.5a Thus, 5-alkyn-1-one 1a
was treated with 2a (5.0 equiv) in the presence of [Rh(OH)-
(cod)]2 (5 mol % of Rh, cod¼cycloocta-1,5-diene) in diox-
ane/H2O (100:1) at room temperature for 5 h under an argon
atmosphere. Chromatographic isolation afforded cyclopen-
tanol 3aa equipped with a tetrasubstituted exocyclic olefin
in 78% yield (Eq. 3). The Z configuration of the exocyclic
double bond was corroborated by a difference NOE study.
Interestingly, the use of 1.5 equiv of 2a was sufficient to
obtain a product yield of 82%. However, a lower catalyst
loading (1–3 mol % of Rh) suffered from a poor reproduc-
ibility, probably due to deterioration of the catalyst.
Table 1. Rhodium(I)-catalyzed reaction of 5-alkyn-l-ones 1 and arylboronic
acids 2a
Entry Substrate 1
ArB(OH)2
2
Product 3
Yield
(%)b
R
MeO2C
MeO2C
R
MeO2C
MeO2C
O
Ar
OH
R'
R'
1
2
3
4
5
6
7
8
9
1a R¼Me R0¼Ph
2b 4-F–C6H4
3ab
76
78
69
77
82
80c
82
72
62
1a
1a
1a
1a
1a
2c 4-NO2–C6H4 3ac
2d 4-Me–C6H4 3ad
2e 3-MeO–C6H4 3ae
2f 3-Cl–C6H4 3af
2g 2-Me–C6H4 3ag
1b R¼n-Bu R0¼Ph 2a Ph
3ba
3ca
3da
1c R¼Me R0¼Me 2a Ph
1d R¼Me R0¼H
2a Ph
2a Ph
Me
Me
MeO2C
Me
2.5 mol%
[Rh(OH)(cod)]2
MeO2C
MeO2C
Me
MeO2C
MeO2C
Ph
OH
O
MeO2C
MeO2C
Ph
OH
Ph
O
MeO2C
PhB(OH)2
10
82
dioxane/H2O
(100/1)
2a
Ph
1e
rt, 5 h
5 equiv
3aa 78%
1a
3ea
1.5 equiv
82%
Me
Me
ð3Þ
O
O
Ph
OH
Ph
3fa
O
11
2a Ph
21
Ph
1f
The proposed reaction pathway is depicted in Scheme 1. A
phenylrhodium(I) species is initially generated by transme-
tallation of hydroxorhodium(I) with 2a. The ketonic carbonyl
group directs the regioselective cis carborhodation across the
carbon–carbon triple bond.9 The resulting alkenylrhodium(I)
intermediate A undergoes intramolecular nucleophilic addi-
tion to the carbonyl group in a 5-exo mode, forming the rho-
dium(I) alkoxide B. Finally, the product 3aa was released by
protodemetalation with regeneration of the catalytically
active hydroxorhodium(I) species. Of note is that carborho-
dation onto the carbon–carbon triple bond and the ketonic
carbonyl group proceeds at room temperature.
a
Reaction conditions:
1
(0.2 mmol), 2 (1.0 mmol), [Rh(OH)(cod)]2
(5 mol % of Rh), dioxane/H2O (2.0 mL/20 mL), room temperature, 2–5 h.
Isolated yield.
A mixture of atropisomers (56:44).
b
c
reaction of substrate 1f with an ether tether gave the product
3fa in only 21% yield due to the lower regioselectivity of the
initial 1,2-addtion of a phenylrhodium(I) species (entry 11).
We assume that the high regioselectivity of the initial 1,2-
addition observed with 1a–1e is to be ascribed not only to
the carbonyl coordination but also to the steric effects of
the two alkyl substituents flanking the carbon–carbon triple
bond. The tether substituent connected to a carbonyl group
through the malonate ester was considerably bulkier than
the other with 1a–1e.10 The corresponding steric contrast
of 1f was not sufficient to cause a regioselective addition.
Me
Ph
trans-
metallation
1a
MeO2C
2a Rh(I)(OH)
Ph Rh(I)
Rh(I)
O
addition
MeO2C
Ph
A
Me
Ph
5-exo-trig
Next, we examined analogous cyclization in a 4-exo-trig
mode (Table 2). Thus, 4-alkyn-1-one 4a having a two-carbon
tether was treated with phenylboronic acid (2a, 5.0 equiv)
under conditions similar to those used for 1. Chromato-
graphic isolation afforded cyclobutanol 5aa in 67% yield
together with a small amount of 1,2-addition product (6%)
(entry 1). It was noteworthy that an intermediate alkenyl-
rhodium(I) species underwent intramolecular nucleophilic
carbonyl addition in a 4-exo-trig mode, although such
four-membered-ring formation would suffer from develop-
ing ring strain. The minor product was formed by the 1,2-
addition of a phenylrhodium(I) species to the carbon–carbon
triple bond with the opposite regiochemistry and subsequent
protonolysis. Similar results were obtained with the reac-
tions of 4-alkyn-1-ones 4b–4d possessing cyclic structures,
which afforded the corresponding bicyclic products 5ba–
5da in 58–61% yield (entries 2–4). The regioselectivities
observed with 4-alkyn-1-ones were generally lower than
those of 5-alkyn-1-ones.
cyclization
H2O
–Rh(I)(OH)
MeO2C
MeO2C
3aa
ORh(I)
Ph
B
Scheme 1.
The results obtained with a variety of 5-alkyn-1-ones 1 and
arylboronic acids 2 are summarized in Table 1. The catalytic
process worked well with a sterically and electronically
diverse array of arylboronic acids 2b–2g to give the corre-
sponding products 3ab–3ag in 69–82% yield (entries 1–6).
5-Alkyn-1-ones 1b and 1c also gave the corresponding prod-
ucts 3ba and 3ca in good yield (entries 7 and 8). In the case
of 5-alkyn-1-al 1d, a phenylrhodium(I) initially formed pref-
erentially added to the carbon–carbon triple bond even in
the presence of an aldehydic carbonyl group to give the
secondary allylic alcohol 3da in 62% yield (entry 9). The

T. Miura et al. / Tetrahedron 63 (2007) 6131–6140
6133
Table 2. Rhodium(I)-catalyzed reaction of 4-alkyn-1-ones 4 and phenyl-
boronic acid (2a)a
alkylation reaction of a b-ketoester with 1-bromo-2-butyne.
Compound 8a was subjected to the standard reaction condi-
tions for 4-alkyn-1-ones, and after 16 h, the 1H NMR spectra
of the crude reaction mixture was measured prior to chroma-
tographic purification. It was suggested that, in addition to
the expected cyclobutanol 9aa, the mixture contained the
ring-opened product 10aa (9aa/10aa¼ca.7:3). Subsequent
purification by silica gel chromatography afforded only
10aa in 69% isolated yield (Scheme 2). Therefore, the reac-
tion is assumed to proceed in a similar manner to that of
4-alkyn-1-ones 4, leading to the initial formation of cyclo-
butanol 9aa. Then, opening of the cyclobutane ring through
a retro-aldol reaction affords the product 10aa. The retro-
aldol reaction is promoted by the acidic nature of silica gel
during purification.
Entry
Substrate 4
Me
Me
Product 5
Yield (%)b
Et
Et
Me
Me
O
Ph
1
67c
HO Ph
Ph
5aa
4a
Me
Ph
O
Me
HO
2
3
58
58
Me
4b
Me
5ba
Et
Ph
HO
O
Et
Me
1
3
4
5
2.5 mol%
[Rh(OH)(cod)]2
Me
EtO2C2
Me
2 equiv
PhB(OH)2
2a
Ph
Me
Me
EtO2C
Me
Rh(I)
O
dioxane/H2O
(100/1)
Me
Ph
O
4c
5ca
rt, 16 h, then H+
Ph
8a
C
Et
Ph
O
Et
HO
Me
Ph
EtO2C
Me
Me
Ph
EtO2C
H2O
H+
4
61
Me
Me
–Rh(I)OH
Ph
Ph OH
ORh(I)
4d
5da
9aa
D
a
Reaction conditions: 4 (0.25 mmol), 2a (1.25 mmol), [Rh(OH)(cod)]2
(5 mol % of Rh), dioxane/H2O (2.5 mL/25 mL), room temperature,
1
OH
EtOC
+
EtO2C
OH
2
3
6–25 h.
Isolated yield.
Obtained as a mixture with 1,2-adduct (6%).
Me
Ph
4
5
b
c
Me
Ph
Me
Ph
EtOC
Me
Ph
–H+
Me
Ph
Me
Ph OH
O
+OH
In the case of 6-alkyn-1-ones 6 having a four-carbon tether,
even the initial 1,2-addition of a phenylrhodium(I) species
failed to occur at room temperature. When the reaction tem-
perature was raised to 100 ꢀC, 1,2-addition took place but
the resultant alkenylrhodium(I) intermediate failed to add
the carbonyl group, giving the hydrolyzed compound 7 as
the major product (Eq. 4).
10aa 69%
E
F
Scheme 2.
During the transformation of 8a to 10aa, a phenyl group was
introduced on the C(5) atom of 8a and the benzoyl group
bound to the C(2) atom of 8a migrated to the C(4) atom of
the product 10aa.11 This acyl 1,3-migration reaction was
applied to a variety of combinations of acetylenic b-ketoest-
ers 8 and arylboronic acids 2 (Table 3). Both electron-rich
Me
Ph
O
2.5 mol%
[Rh(OH)(cod)]2
MeO2C
MeO2C
Me
5 equiv
PhB(OH)2
MeO2C
MeO2C
H
dioxane/H2O
(100/1)
100 °C, 2 h
ð4Þ
O
2a
Table 3. Rhodium(I)-catalyzed acyl 1,3-migration in the reaction of acetyl-
enic b-ketoesters 8 with arylboronic acids 2a
Me
Me
7 38%
6
Entry Substrate 8
ArB(OH)2
2
Product 10
Yield (%)b
EtO2C
EtO2C
R
The contrasting results obtained with 1, 4, and 6 indicated
that, with alkynones 1 and 4, coordination of the carbonyl
group to rhodium facilitates the 1,2-addition to the alkyne
moiety and subsequent intramolecular nucleophilic addition
to the carbonyl group and that the accelerating effect by co-
ordination significantly depends on the tether length.5e Of
note was that the four-membered ring formation was facile
whereas the six-membered ring formation failed.
R
Me
R'
Me
R'
O
Ar
O
1
2
3
4
5
6
7
8a R¼Me R0¼Ph 2b 4-F–C6H4
10ab
2d 4-Me–C6H4 10ad
2e 3-MeO–C6H4 10ae
63
75
77
66
92
67
25
8a
8a
8a
2f 3-Cl–C6H4
10af
10ba
10ca
10da
8b R¼Et R0¼Ph 2a Ph
8c R¼Et R0¼Me 2a Ph
8d R¼TMS R0¼Ph 2a Ph
2.2. Arylative acyl 1,3-migration of acetylenic
b-ketoesters
a
Reaction conditions: 8 (0.2 mmol), 2 (0.6–1.0 mmol), [Rh(OH)(cod)]2
(5 mol % of Rh), dioxane/H2O (2.0 mL/20 mL), room temperature, 5 h;
then treatment with aq NH4Cl.
We next synthesized acetylenic b-ketoesters 8 as the sub-
strate containing a 4-alkyn-1-one substructure by a simple
b
Isolated yield.

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T. Miura et al. / Tetrahedron 63 (2007) 6131–6140
Table 4. Rhodium(I)-catalyzed two-carbon-atom ring expansion of acetyl-
enic b-ketoesters 11 with phenylboronic acid (2a)a
and -deficient arylboronic acids were suitably reactive (en-
tries 1–4). In the case of o-tolylboronic acid (2g), however,
the alkenylrhodium(I) intermediate was not reactive enough
to add the benzoyl group probably due to steric reasons, af-
fording a simple 1,2-adduct. Substituents at the alkyne ter-
mini were also examined. A better yield was obtained with
ethyl-substituted 8b than with methyl-substituted 8a (entry
5). Methyl ketone 8c also underwent the acyl 1,3-migration
(entry 6). The reaction of trimethylsilyl-substituted alkyne
8d suffered from lower regioselectivity of the initial 1,2-
addition to give the product 10da in only 25% yield (entry
7). We assume that the increased steric bulkiness of the
trimethylsilyl group deteriorated the regioselectivity.
Entry
Substrate 11
Product 12
Yield (%)b
Ph
O
Me
O
Me
1
51
CO2Et
CO2Et
11b
12ba
Ph
O
O
Me
Me
CO2Et
2
3
4
5
49
58
CO2Et
12ca
11c
Acetylenic b-ketoesters 8e having an active hydrogen failed
to undergo the cyclization reaction, probably because of the
predominance of a stable enol tautomer (Fig. 1).
Ph
O
Me
O
Me
CO2Et
Et
EtO2C
H
CO2Et
O
11d
12da
Ph
Ph
8e
O
8
O
Me
Me
Figure 1.
CO2Et
54c
10
CO2Et
We next envisioned that, if the 4-alkyn-1-one substructure
was installed in a cyclic skeleton, an analogous acyl 1,3-
migration process would expand the ring by two carbons
to serve as a synthetic method of medium-sized ring carbo-
cyclic skeletons.12,13 Thus, the cyclic substrate 11a was
reacted with phenylboronic acid (2a) under the similar reac-
tion conditions. The resulting reaction mixture was suc-
cessively treated with aq NH4Cl for 24 h to promote a
retro-aldol process. As expected, the cycloheptanone 12aa
was produced in 63% isolated yield through the arylative
cyclization and the following ring expansion (Scheme 3).
11e
12ea
O
Me
O
Me
Me
57
Me
O
O
Ph
11f
12fa
O
Me
Me
Me
O
O
Me
Ph
6
66
Me
Ph
HO
2.5 mol%
[Rh(OH)(cod)]2
O
O
5 equiv
PhB(OH)2
Me
11g
12ga
+
CO2Et
11a
dioxane/H2O
(100/1)
OEt
a
2a
Reaction conditions: 11 (0.2 mmol), 2a (1.0 mmol), [Rh(OH)(cod)]2
(5 mol % of Rh), dioxane/H2O (2.0 mL/20 mL), room temperature,
rt, 6 h, then H+
O
3–24 h; then treatment with aq NH4Cl.
Isolated yield.
100 ꢀC.
b
c
Ph
Me
O
H+
ring-opening reaction of intermediate cyclobutanols formed
from substrates 11c, 11d, and 11f proceeded more slowly
than that of 11a under the weakly acidic conditions, and
thus, required longer period of time for completion.
CO2Et
12aa 63%
Scheme 3.
As listed in Table 4, the catalytic ring-expansion process
worked well with substrates of five-, six-, and eight-mem-
bered-ring structures 11b–11e to give the corresponding
seven-, eight-, and ten-membered ring products 12ba–12ea
in 49–58% yield (entries 1–4). In addition to the major prod-
ucts 12, the simple 1,2-adducts to the carbon–carbon triple
bond with both regiochemistries were obtained as by-prod-
ucts. Cyclic 1,3-diketones 11f and 11g also underwent the
analogous ring-expansion reaction (entries 5 and 6). The
3. Conclusion
We have developed new cyclization reactions of alkynones
induced by the rhodium-catalyzed regioselective addition
of an arylrhodium(I) species across the carbon–carbon triple
bond at room temperature. An alkenylrhodium(I) intermedi-
ate subsequently undergoes intramolecular carbonyl addi-
tion in 4-exo and 5-exo-trig modes to construct the
carbocyclic alcohols under similar reaction conditions. An

T. Miura et al. / Tetrahedron 63 (2007) 6131–6140
6135
addition reaction of ordinary alkynes with arylboronic acids
requires heating over 80 ꢀC.4,9 The presence of the carbonyl
group as the secondary acceptor functionality greatly con-
tributes to the high reactivity. This method has been applied
to a new acyl 1,3-migration reaction and a two-carbon-atom
ring-expansion reaction, which gives a convenient access to
medium-sized ring compounds.
73.1, 79.9, 169.6, 198.7; HRMS (CI) calcd for C11H15O5
(M+H+) 227.0919, found 227.0915.
4.2.5. Dimethyl 2-(but-2-ynyl)-2-(2-oxo-cyclopentyl)mal-
onate (1e). IR (neat) 2955, 1723, 1435, 1245, 1145,
1048 cmꢁ1 1H NMR d 1.66–1.99 (m, 2H), 1.76 (t,
;
J¼2.7 Hz, 3H), 2.01–2.13 (m, 1H), 2.17–2.41 (m, 3H),
2.78 (dq, J¼16.8, 2.6 Hz, 1H), 2.89 (dq, J¼17.0, 2.6 Hz,
1H), 2.92–3.01 (m, 1H), 3.755 (s, 3H), 3.764 (s, 3H); 13C
NMR d 3.6, 20.6, 24.4, 26.6, 37.9, 52.6, 52.7, 52.8, 58.5,
74.2, 78.9, 169.7, 170.3, 216.5; HRMS (CI) calcd for
C14H19O5 (M+H+) 267.1232, found 267.1235.
4. Experimental
4.1. General
All manipulations were carried out with standard Schlenk
technique under an argon atmosphere. Preparative thin layer
chromatography was performed with silica gel 60 PF254
(Merck). 1H and 13C NMR spectra were recorded on a Varian
Gemini 2000 (1H at 300.07 MHz and 13C at 75.46 MHz)
spectrometer. NMR data were obtained in CDCl3 otherwise
noted. Proton chemical shifts were referenced to the residual
proton signal of the solvent at 7.26 ppm. Carbon chemical
shifts were referenced to the carbon signal of the solvent
at 77.00 ppm. High resolution mass spectra were recorded
on a JOEL JMS-SX102A spectrometer. IR spectra were
recorded on a Shimadzu FTIR-8100 spectrometer. 1,4-Diox-
ane was distilled over sodium benzophenone ketyl prior to
use. All other commercially available chemical resources
were used without further purifications.
4.2.6. But-2-ynyloxymethyl phenyl ketone (1f). IR (Nujol)
2923, 1701, 1449, 1229, 1157, 1121 cmꢁ1; 1H NMR d 1.86
(t, J¼2.3 Hz, 3H), 4.32 (q, J¼2.4 Hz, 2H), 4.85 (s, 2H),
7.43–7.52 (m, 2H), 7.55–7.63 (m, 1H), 7.91–7.98 (m, 2H);
13C NMR d 3.4, 58.8, 71.4, 74.1, 83.5, 127.6, 128.5, 133.3,
134.6, 195.6; HRMS (FAB) calcd for C12H13O2 (M+H+)
189.0916, found 189.0909.
4.2.7. 2,2-Dimethyl-1-phenylhept-4-yn-1-one (4a). IR
(neat) 2975, 1678, 1468, 1320, 1215, 1159 cmꢁ1; 1H NMR
d 1.09 (t, J¼7.5 Hz, 3H), 1.39 (s, 6H), 2.14 (qt, J¼7.6,
2.4 Hz, 2H), 2.52 (t, J¼2.6 Hz, 2H), 7.35–7.49 (m, 3H),
7.60–7.67 (m, 2H); 13C NMR d 12.4, 14.2, 25.3, 30.4,
47.8, 76.1, 84.4, 127.3, 128.0, 130.6, 139.0, 208.3; HRMS
(CI) calcd for C15H19O (M+H+) 215.1436, found 215.1438.
4.2. Starting materials
4.2.8. 2-(But-2-ynyl)-2-methylcyclohexanone (4b). IR
(neat) 2936, 1709, 1453, 1375, 1127, 1073 cmꢁ1; 1H NMR
d 1.18 (s, 3H), 1.67–1.96 (m, 9H), 2.25–2.50 (m, 4H); 13C
NMR d 3.5, 21.2, 22.5, 27.4, 27.9, 38.0, 38.6, 48.2, 75.4,
78.0, 214.5; HRMS (CI) calcd for C11H17O (M+H+)
165.1279, found 165.1277.
4.2.1. Dimethyl 2-(but-2-ynyl)-2-(2-oxo-2-phenylethyl)-
malonate (1a). IR (neat) 2955, 1740, 1688, 1435, 1291,
1
1208 cmꢁ1; H NMR d 1.71 (t, J¼2.4 Hz, 3H), 3.04 (q,
J¼2.5 Hz, 2H), 3.76 (s, 6H), 3.89 (s, 2H), 7.44–7.52 (m,
2H), 7.56–7.63 (m, 1H), 7.98–8.04 (m, 2H); 13C NMR
d 3.5, 23.8, 41.1, 53.1, 54.9, 73.7, 79.4, 128.1, 128.6, 133.4,
136.4, 170.1, 196.8; HRMS (EI) calcd for C17H18O5 (M+)
302.1154, found 302.1155.
4.2.9. 2-Methyl-2-(pent-2-ynyl)indan-1-one (4c). IR (neat)
2975, 1715, 1609, 1466, 1374, 1300 cmꢁ1; 1H NMR d 0.93
(t, J¼7.5 Hz, 3H), 1.27 (s, 3H), 2.02 (qt, J¼7.5, 2.4 Hz, 2H),
2.40 (t, J¼2.6 Hz, 2H), 2.92 (d, J¼17.1 Hz, 1H), 3.35 (d,
J¼17.1 Hz, 1H), 7.33–7.40 (m, 1H), 7.42–7.48 (m, 1H),
7.60 (td, J¼7.2, 1.2 Hz, 1H), 7.73–7.78 (m, 1H); 13C NMR
d 12.3, 14.1, 23.3, 28.0, 40.1, 48.8, 75.6, 83.6, 124.3,
126.5, 127.3, 134.9, 135.7, 152.8, 209.8; HRMS (EI) calcd
for C15H16O (M+) 212.1201, found 212.1200.
4.2.2. Dimethyl 2-(hept-2-ynyl)-2-(2-oxo-2-phenylethyl)-
malonate (1b). IR (neat) 2955, 1743, 1688, 1435, 1291,
1
1207 cmꢁ1; H NMR d 0.84 (t, J¼7.1 Hz, 3H), 1.22–1.45
(m, 4H), 2.02–2.13 (m, 2H), 3.05 (t, J¼2.4 Hz, 2H), 3.76
(s, 6H), 3.90 (s, 2H), 7.43–7.53 (m, 2H), 7.55–7.63 (m,
1H), 7.98–8.06 (m, 2H); 13C NMR d 13.6, 18.3, 21.8, 23.8,
30.9, 41.1, 53.0, 55.0, 74.6, 84.1, 128.1, 128.6, 133.4, 136.4,
170.1, 196.8; HRMS (CI) calcd for C20H25O5 (M+H+)
345.1702, found 345.1706.
4.2.10. 2-Methyl-2-(pent-2-ynyl)-3,4-dihydro-2H-naph-
thalen-1-one (4d). IR (neat) 2934, 1682, 1601, 1456,
1
1323, 1221 cmꢁ1; H NMR d 1.10 (t, J¼7.5 Hz, 3H), 1.25
(s, 3H), 2.06 (dt, J¼13.6, 5.6 Hz, 1H), 2.16 (qt, J¼7.4,
2.4 Hz, 2H), 2.25 (ddd, J¼13.5, 8.4, 6.0 Hz, 1H), 2.45 (dt,
J¼16.6, 2.4 Hz, 1H), 2.53 (dt, J¼16.8, 2.4 Hz, 1H), 2.90–
3.10 (m, 2H), 7.23 (d, J¼7.8 Hz, 1H), 7.30 (t, J¼7.7 Hz,
1H), 7.46 (td, J¼7.5, 1.4 Hz, 1H), 8.04 (dd, J¼7.5, 1.2 Hz,
1H); 13C NMR d 12.5, 14.3, 21.4, 25.5, 27.4, 33.1, 44.6,
75.6, 84.3, 126.6, 128.0, 128.7, 131.3, 133.1, 143.4, 201.4;
HRMS (EI) calcd for C16H18O (M+) 226.1358, found
226.1358.
4.2.3. Dimethyl 2-(but-2-ynyl)-2-(2-oxo-propyl)malonate
(1c). IR (Nujol) 2909, 1748, 1715, 1291, 1258,
1
1204 cmꢁ1; H NMR d 1.75 (t, J¼2.7 Hz, 3H), 2.18 (s,
3H), 2.92 (q, J¼2.5 Hz, 2H), 3.32 (s, 2H), 3.72 (s, 6H);
13C NMR d 3.5, 23.8, 30.2, 45.5, 53.0, 54.7, 73.6, 79.2,
169.9, 205.4; HRMS (CI) calcd for C12H17O5 (M+H+)
241.1076, found 241.1075.
4.2.4. Dimethyl 2-(but-2-ynyl)-2-(2-oxo-ethyl)malonate
(1d). IR (Nujol) 2757, 1737, 1291, 1200, 1092,
4.2.11. Ethyl 2-benzoyl-2-methylhex-4-ynoate (8a). IR
(neat) 2984, 1738, 1686, 1449, 1244, 1100 cmꢁ1; 1H NMR
d 1.09 (t, J¼7.2 Hz, 3H), 1.64 (s, 3H), 1.74 (t, J¼2.6 Hz,
3H), 2.77–2.93 (m, 2H), 4.06–4.23 (m, 2H), 7.36–7.46 (m,
1
1057 cmꢁ1; H NMR d 1.74 (t, J¼2.6 Hz, 3H), 2.90 (q,
J¼2.5 Hz, 2H), 3.21 (d, J¼1.2 Hz, 2H), 3.75 (s, 6H), 9.74
(t, J¼1.1 Hz, 1H); 13C NMR d 3.5, 24.4, 46.2, 53.2, 54.3,

6136
T. Miura et al. / Tetrahedron 63 (2007) 6131–6140
2H), 7.48–7.56 (m, 1H), 7.79–7.86 (m, 2H); 13C NMR d 3.5,
13.8, 21.1, 27.3, 57.0, 61.6, 73.7, 79.2, 128.4, 132.7, 135.4,
172.9, 196.5; HRMS (CI) calcd for C16H19O3 (M+H+)
259.1334, found 259.1335.
4.2.18. Ethyl 2-(but-2ynyl)-1-oxo-3,4-dihydro-2H-naph-
thalene-2-carboxylate (11d). IR (neat) 2980, 1732, 1690,
1601, 1455, 1238 cmꢁ1
;
1H NMR d 1.16 (t, J¼7.2 Hz,
3H), 1.73 (t, J¼2.6 Hz, 3H), 2.43 (ddd, J¼13.7, 10.7,
4.9 Hz, 1H), 2.62 (dt, J¼13.7, 4.8 Hz, 1H), 2.84 (q,
J¼2.5 Hz, 2H), 2.96 (dt, J¼17.4, 5.0 Hz, 1H), 3.15 (ddd,
J¼17.4, 10.8, 4.8 Hz, 1H), 4.15 (q, J¼7.0 Hz, 2H), 7.19–
7.26 (m, 1H), 7.27–7.35 (m, 1H), 7.48 (td, J¼7.5, 1.5 Hz,
1H), 8.05 (dd, J¼8.0, 1.4 Hz, 1H); 13C NMR d 3.6, 14.0,
24.6, 25.9, 30.6, 57.0, 61.5, 74.2, 78.6, 126.7, 128.1,
128.7, 131.8, 133.5, 143.3, 170.9, 194.1; HRMS (EI) calcd
for C17H18O3 (M+) 270.1256, found 270.1255.
4.2.12. Ethyl 2-benzoyl-2-methylhept-4-ynoate (8b). IR
(neat) 2979, 1738, 1683, 1449, 1244, 1100 cmꢁ1; 1H NMR
d 1.07 (t, J¼7.5 Hz, 3H), 1.10 (t, J¼7.2 Hz, 3H), 1.64 (s,
3H), 2.12 (qt, J¼7.4, 2.4 Hz, 2H), 2.79–2.94 (m, 2H),
4.06–4.23 (m, 2H), 7.37–7.46 (m, 2H), 7.48–7.56 (m, 1H),
7.79–7.87 (m, 2H); 13C NMR d 12.3, 13.8, 14.1, 21.0,
27.2, 57.0, 61.5, 73.9, 85.3, 128.4, 132.7, 135.4, 172.8,
196.4; HRMS (CI) calcd for C17H21O3 (M+H+) 273.1491,
found 273.1490.
4.2.19. Ethyl 1-(but-2-ynyl)-2-oxocyclooctane-1-carboxy-
late (11e). IR (neat) 2930, 1736, 1707, 1466, 1204 cmꢁ1
;
4.2.13. Ethyl 2-acetyl-2-methylhept-4-ynoate (8c). IR
(neat) 2983, 1742, 1717, 1237, 1192, 1107 cmꢁ1; 1H NMR
d 1.08 (t, J¼7.5 Hz, 3H), 1.26 (t, J¼7.2 Hz, 3H), 1.45 (s,
3H), 2.12 (qt, J¼7.5, 2.4 Hz, 2H), 2.18 (s, 3H), 2.61–2.76
(m, 2H), 4.12–4.29 (m, 2H); 13C NMR d 12.3, 14.0, 14.1,
19.1, 25.3, 26.1, 59.2, 61.5, 74.1, 84.9, 171.7, 204.1;
HRMS (CI) calcd for C12H19O3 (M+H+) 211.1334, found
211.1337.
1H NMR d 0.82–0.99 (m, 1H), 1.23 (t, J¼7.1 Hz, 3H),
1.27–1.93 (m, 7H), 1.75 (t, J¼2.7 Hz, 3H), 2.16–2.29 (m,
2H), 2.42 (dq, J¼17.2, 2.5 Hz, 1H), 2.49–2.63 (m, 1H),
2.78 (td, J¼12.0, 3.7 Hz, 1H), 2.92–3.03 (m, 1H), 4.12–
4.24 (m, 2H); 13C NMR d 3.5, 14.0, 21.3, 23.1, 24.3, 25.5,
27.8, 29.3, 38.3, 61.5, 62.5, 74.4, 78.2, 170.4, 211.1;
HRMS (EI) calcd for C15H22O3 (M+) 250.1569, found
250.1569.
4.2.14. Ethyl 2-benzoyl-2-methyl-5-trimethylsilylpent-
4-ynoate (8d). IR (neat) 2960, 1740, 1686, 1250, 1194,
4.2.20. 2-(But-2-ynyl)-2-methylindane-1,3-dione (11f). IR
(Nujol) 1744, 1713, 1597, 1455, 1264, 1184 cmꢁ1; 1H NMR
d 1.26 (s, 3H), 1.41 (t, J¼2.4 Hz, 3H), 2.60 (q, J¼2.5 Hz,
2H), 7.82–7.89 (m, 2H), 7.96–8.04 (m, 2H); 13C NMR
d 3.1, 18.7, 24.8, 53.3, 73.5, 79.0, 123.3, 135.7, 141.5,
203.1; HRMS (EI) calcd for C14H12O2 (M+) 212.0837,
found 212.0842.
1
1100 cmꢁ1; H NMR d 0.12 (s, 9H), 1.12 (t, J¼7.2 Hz,
3H), 1.66 (s, 3H), 2.88 (d, J¼17.4 Hz, 1H), 2.96 (d,
J¼17.1 Hz, 1H), 4.06–4.25 (m, 2H), 7.37–7.45 (m, 2H),
7.49–7.56 (m, 1H), 7.79–7.86 (m, 2H); 13C NMR d 0.0,
13.9, 21.1, 28.3, 57.0, 61.7, 88.5, 101.7, 128.4, 132.7,
135.4, 172.4, 196.2; HRMS (CI) calcd for C18H25O3Si
(M+H+) 317.1573, found 317.1573.
4.2.21. 2-(But-2-ynyl)-2-methyl-cyclohexane-1,3-dione
(11g). IR (Nujol) 1725, 1700, 1325, 1208, 1100,
1
4.2.15. Ethyl 1-(but-2-ynyl)-2-oxocyclopentane-1-car-
boxylate (11a). IR (neat) 2980, 1751, 1727, 1229,
1028 cmꢁ1; H NMR d 1.26 (s, 3H), 1.69–1.73 (m, 3H),
1.87–2.08 (m, 2H), 2.55–2.60 (m, 2H), 2.65–2.73 (m, 4H);
13C NMR d 3.4, 17.2, 21.3, 26.0, 38.3, 64.1, 74.6, 78.3,
209.4; HRMS (EI) calcd for C11H14O2 (M+) 178.0994,
found 178.0990.
1
1157 cmꢁ1; H NMR d 1.24 (t, J¼7.1 Hz, 3H), 1.74 (t,
J¼2.3 Hz, 3H), 1.94–2.13 (m, 2H), 2.19–2.35 (m, 2H),
2.39–2.53 (m, 2H), 2.65 (q, J¼2.6 Hz, 2H), 4.15 (q,
J¼7.1 Hz, 2H); 13C NMR d 3.5, 14.1, 19.8, 23.6, 32.6,
38.4, 59.1, 61.6, 74.4, 78.0, 170.6, 214.2; HRMS (CI) calcd
for C12H17O3 (M+H+) 209.1178, found 209.1175.
4.3. General procedure for arylative cyclization of
5-alkyn-1-ones 1
4.2.16. Ethyl 2-(but-2-ynyl)-1-oxoindane-2-carboxylate
(11b). IR (Nujol) 1730, 1705, 1605, 1285, 1254,
To an oven-dried, Ar-purged flask were added [Rh(OH)-
(cod)]2 (2.28 mg, 5 mmol, 5 mol % of Rh), arylboronic
acid 2 (1.0 mmol, 5.0 equiv), and 1,4-dioxane (1 mL). A so-
lution of substrate 1 (0.2 mmol, 1.0 equiv) in 1,4-dioxane
(1.0 mL) and H2O (20 mL) was added to the reaction mixture
at room temperature. After complete consumption of sub-
strate was observed, water was added. The aqueous layer
was extracted with ethyl acetate three times. The combined
extracts were washed with brine and dried over MgSO4. The
solvent was removed under reduced pressure and the residue
was purified by preparative thin layer chromatography
(hexane/ethyl acetate) to give the product 3.
1
1188 cmꢁ1; H NMR d 1.19 (t, J¼7.1 Hz, 3H), 1.56 (t,
J¼2.6 Hz, 3H), 2.77 (dq, J¼16.5, 2.5 Hz, 1H), 2.93 (dq,
J¼16.6, 2.5 Hz, 1H), 3.36 (d, J¼17.4 Hz, 1H), 3.68 (d,
J¼17.4 Hz, 1H), 4.07–4.23 (m, 2H), 7.35–7.43 (m, 1H),
7.48–7.53 (m, 1H), 7.56–7.67 (m, 1H), 7.77 (d, J¼7.8 Hz,
1H); 13C NMR d 3.3, 14.0, 24.5, 36.8, 59.6, 61.8, 73.9,
77.9, 124.7, 126.2, 127.6, 135.2, 135.3, 153.5, 170.2,
201.5; HRMS (CI) calcd for C16H17O3 (M+H+) 257.1178,
found 257.1180.
4.2.17. Ethyl 1-(but-2-ynyl)-2-oxocyclohexane-1-carb-
oxylate (11c). IR (neat) 2945, 1717, 1443, 1192, 1092,
4.3.1. 1,1-Dimethoxycarbonyl-3-hydroxy-3-phenyl-4-
[(Z)-1-phenylethylidene]cyclopentane (3aa). IR (Nujol)
1
1022 cmꢁ1; H NMR d 1.26 (t, J¼7.2 Hz, 3H), 1.52–1.85
(m, 4H), 1.75 (t, J¼2.7 Hz, 3H), 1.95–2.09 (m, 1H), 2.35–
2.53 (m, 3H), 2.60–2.75 (m, 2H), 4.21 (q, J¼7.1 Hz, 2H);
13C NMR d 3.6, 14.1, 22.4, 25.1, 27.4, 35.4, 40.9, 60.3,
61.5, 74.0, 78.7, 170.6, 206.4; HRMS (EI) calcd for
C13H18O3 (M+) 222.1256, found 222.1257.
3546, 2920, 1732, 1444, 1240, 1202 cmꢁ1 1H NMR
;
d 2.00 (br s, 3H), 2.45 (s, 1H), 2.70 (d, J¼14.1 Hz, 1H),
2.76 (dd, J¼14.1, 1.5 Hz, 1H), 3.13 (dq, J¼17.0, 1.9 Hz,
1H), 3.63 (d, J¼16.5 Hz, 1H), 3.70 (s, 3H), 3.82 (s, 3H),
6.63–6.71 (m, 2H), 6.87–7.03 (m, 8H); 13C NMR d 23.9,

T. Miura et al. / Tetrahedron 63 (2007) 6131–6140
6137
40.5, 52.9, 53.0, 53.2, 57.5, 82.0, 125.2, 125.9, 126.0, 127.2,
127.5, 127.7, 134.9, 141.5, 141.9, 146.1, 171.8, 172.7;
HRMS (FAB) calcd for C23H24O5 (M+) 380.1624, found
380.1624.
(s, 3H), 6.59–6.64 (m, 2H), 6.81–6.92 (m, 2H), 6.95–7.06
(m, 5H); 13C NMR d 23.5, 40.4, 53.0, 53.1, 53.4, 57.5,
81.9, 125.1, 125.9, 126.1, 127.2, 128.2, 128.5, 133.1,
133.7, 142.4, 143.5, 145.3, 171.7, 173.1; HRMS (FAB) calcd
for C23H23ClO5 (M+) 414.1234, found 414.1234.
4.3.2. 1,1-Dimethoxycarbonyl-3-hydroxy-3-phenyl-4-
[(Z)-1-(4-fluorophenyl)ethylidene]cyclopentane (3ab).
4.3.7. 1,1-Dimethoxycarbonyl-3-hydroxy-3-phenyl-4-
[(Z)-1-(2-methylphenyl)ethylidene]cyclopentane (3ag).
A mixture of atropisomers (56:44). IR (Nujol) 3530, 1736,
1
IR (Nujol) 3555, 1732, 1509, 1260, 1254, 1213 cmꢁ1; H
NMR d 1.96 (br s, 3H), 2.64–2.72 (m, 2H), 2.75 (dd,
J¼14.4, 1.8 Hz, 1H), 3.15 (dq, J¼17.3, 2.0 Hz, 1H), 3.59
(d, J¼17.1 Hz, 1H), 3.72 (s, 3H), 3.83 (s, 3H), 6.54–6.68
(m, 4H), 6.94–7.05 (m, 5H); 13C NMR d 23.9, 40.5,
52.9, 53.1, 53.5, 57.5, 82.0, 114.2 (d, J¼20.9 Hz), 125.2,
126.0, 127.2, 129.5 (d, J¼8.1 Hz), 134.1, 137.7 (d, J¼
3.5 Hz), 142.0, 145.8, 161.0 (d, J¼244.7 Hz), 171.7,
173.2; HRMS (FAB) calcd for C23H23FO5 (M+) 398.1530,
found 398.1531.
1458, 1238, 1203, 1063 cmꢁ1
;
1H NMR d 1.59 (s,
1.680H), 1.90 (br s, 1.680H), 1.94 (br s, 1.320H), 2.19 (s,
0.440H), 2.24 (s, 1.320H), 2.52 (s, 0.560H), 2.68–2.86 (m,
2H), 3.03 (dq, J¼16.8, 2.1 Hz, 0.560H), 3.12 (dq, J¼16.4,
2.0 Hz, 0.440H), 3.57–3.74 (m, 1H), 3.66 (s, 1.320H), 3.78
(s, 1.680H), 3.80 (s, 1.320H), 3.84 (s, 1.680H), 6.01 (dd,
J¼7.5, 1.2 Hz, 0.440H), 6.51 (t, J¼7.7 Hz, 0.440H), 6.55–
6.62 (m, 0.560H), 6.83–7.16 (m, 7.560H); 13C NMR
d 19.2, 19.4, 22.4, 22.9, 40.2, 40.6, 52.6, 52.8, 52.9, 53.0,
57.4, 57.6, 81.5, 81.8, 124.6, 124.7, 124.99, 125.05, 125.6,
126.2, 126.4, 126.8, 127.0, 127.5, 128.2, 128.3, 129.5,
129.8, 133.7, 134.4, 134.8, 135.0, 140.5, 140.8, 140.9,
141.8, 144.5, 147.7, 171.5, 172.0, 172.3, 172.7; HRMS
(FAB) calcd for C24H25O5 (MꢁH+) 393.1702, found
393.1701.
4.3.3. 1,1-Dimethoxycarbonyl-3-hydroxy-3-phenyl-4-
[(Z)-1-(4-nitrophenyl)ethylidene]cyclopentane (3ac). IR
(Nujol) 3528, 1732, 1597, 1518, 1347, 1256 cmꢁ1 1H
;
NMR (C6D6) d 1.60 (br s, 3H), 2.74 (d, J¼14.4 Hz, 1H),
2.88 (dd, J¼14.3, 2.3 Hz, 1H), 3.18–3.29 (m, 2H), 3.32 (s,
3H), 3.39 (s, 3H), 3.63 (d, J¼17.7 Hz, 1H), 6.45–6.52 (m,
2H), 6.68–6.75 (m, 3H), 6.83–6.90 (m, 2H), 7.53–7.59 (m,
2H); 13C NMR (C6D6) d 23.0, 40.9, 52.6, 52.9, 54.4, 58.0,
82.1, 122.3, 125.7, 126.3, 127.5, 129.3, 133.2, 143.9,
145.4, 146.3, 148.7, 171.4, 173.9; HRMS (FAB) calcd for
C23H23NO7 (M+) 425.1475, found 425.1472.
4.3.8. 1,1-Dimethoxycarbonyl-3-hydroxy-3-phenyl-4-
[(Z)-1-phenylpentylidene]cyclopentane (3ba). IR (neat)
3570, 2955, 1732, 1447, 1255, 1067 cmꢁ1 1H NMR
;
d 0.87 (t, J¼6.8 Hz, 3H), 1.18–1.44 (m, 4H), 2.14–2.41
(m, 3H), 2.69 (d, J¼14.1 Hz, 1H), 2.75 (d, J¼14.4 Hz,
1H), 3.08 (d, J¼16.5 Hz, 1H), 3.63–3.73 (m, 4H), 3.82 (s,
3H), 6.53–6.61 (m, 2H), 6.86–7.07 (m, 8H); 13C NMR
d 14.0, 22.6, 29.3, 37.1, 40.1, 52.85, 52.90, 57.6, 81.9,
125.0, 125.8, 125.9, 127.2, 127.4, 128.3, 139.7, 140.4,
142.0, 146.6, 171.8, 172.4; HRMS (FAB) calcd for
C26H30O5 (M+) 422.2093, found 422.2092.
4.3.4. 1,1-Dimethoxycarbonyl-3-hydroxy-3-phenyl-4-
[(Z)-1-(4-methylphenyl)ethylidene]cyclopentane (3ad).
1
IR (Nujol) 3546, 1733, 1514, 1247, 1200, 1092 cmꢁ1; H
NMR d 1.98 (br s, 3H), 2.16 (s, 3H), 2.40 (s, 1H), 2.71 (d,
J¼14.1 Hz, 1H), 2.76 (dd, J¼14.1, 1.2 Hz, 1H), 3.13 (dq,
J¼16.8, 1.8 Hz, 1H), 3.61 (d, J¼16.8 Hz, 1H), 3.67 (s,
3H), 3.82 (s, 3H), 6.55 (d, J¼7.8 Hz, 2H), 6.73 (d,
J¼7.8 Hz, 2H), 6.97–7.05 (m, 5H); 13C NMR d 21.0, 23.9,
40.4, 52.8, 53.0, 57.4, 82.1, 125.3, 125.9, 127.2, 127.5,
128.2, 134.7, 135.6, 138.9, 141.2, 146.4, 171.8, 172.6;
HRMS (FAB) calcd for C24H26O5 (M+) 394.1780, found
394.1778.
4.3.9. 1,1-Dimethoxycarbonyl-3-hydroxy-3-methyl-4-
[(Z)-1-phenylethylidene]cyclopentane (3ca). IR (neat)
3520, 2955, 1732, 1435, 1258, 1071 cmꢁ1; 1H NMR d 0.88
(s, 3H), 1.95 (t, J¼1.5 Hz, 3H), 2.16 (br s, 1H), 2.33 (d,
J¼13.8 Hz, 1H), 2.54 (dd, J¼14.0, 2.0 Hz, 1H), 2.95 (dq,
J¼17.4, 1.7 Hz, 1H), 4.40 (d, J¼17.3 Hz, 1H), 3.76 (s,
3H), 3.79 (s, 3H), 7.15–7.35 (m, 5H); 13C NMR d 24.1,
27.3, 39.7, 50.5, 52.8, 52.9, 56.5, 78.1, 126.7, 128.0,
128.2, 133.2, 139.0, 142.9, 172.1, 173.1; HRMS (FAB) calcd
for C18H21O4 (MꢁOH+) 301.1440, found 301.1440.
4.3.5. 1,1-Dimethoxycarbonyl-3-hydroxy-3-phenyl-4-
[(Z)-1-(3-methoxyphenyl)ethylidene]cyclopentane (3ae).
1
IR (neat) 3563, 2955, 1733, 1597, 1457, 1067 cmꢁ1; H
NMR d 1.99 (br s, 3H), 2.48 (s, 1H), 2.71 (dd, J¼14.3,
0.8 Hz, 1H), 2.77 (dd, J¼14.1, 1.5 Hz, 1H), 3.13 (dq,
J¼17.1, 2.1 Hz, 1H), 3.50 (s, 3H), 3.61 (d, J¼17.1 Hz,
1H), 3.68 (s, 3H), 3.82 (s, 3H), 6.12 (dd, J¼2.4, 1.5 Hz,
1H), 6.33–6.39 (m, 1H), 6.47–6.55 (m, 1H), 6.86–6.95 (m,
1H), 6.96–7.09 (m, 5H); 13C NMR d 23.7, 40.4, 52.8, 52.9,
53.0, 54.8, 57.4, 82.0, 112.66, 112.71, 119.8, 125.3, 125.9,
127.2, 128.7, 134.5, 141.4, 143.2, 146.4, 158.7, 171.7,
172.6; HRMS (FAB) calcd for C24H26O6 (M+) 410.1729,
found 410.1728.
4.3.10. 1,1-Dimethoxycarbonyl-3-hydroxy-4-[(Z)-1-phe-
nylethylidene]cyclopentane (3da). IR (neat) 3526, 2953,
1732, 1435, 1257, 1082 cmꢁ1
;
1H NMR d 1.96 (d,
J¼4.2 Hz, 1H), 2.02 (br s, 3H), 2.37 (dd, J¼14.1, 5.1 Hz,
1H), 2.47 (d, J¼14.1 Hz, 1H), 2.92 (dq, J¼17.7, 1.5 Hz,
1H), 3.39 (d, J¼17.7 Hz, 1H), 3.76 (s, 3H), 3.79 (s, 3H),
4.45–4.53 (m, 1H), 7.21–7.37 (m, 5H); 13C NMR d 21.6,
37.5, 43.0, 52.9, 53.0, 58.3, 72.2, 126.9, 127.5, 128.2,
134.1, 138.0, 142.5, 172.2, 173.3; HRMS (FAB) calcd for
C17H20O5 (M+) 304.1311, found 304.1304.
4.3.6. 1,1-Dimethoxycarbonyl-3-hydroxy-3-phenyl-4-
[(Z)-1-(3-chlorophenyl)ethylidene]cyclopentane (3af).
1
IR (neat) 3505, 2958, 1735, 1593, 1436, 1068 cmꢁ1; H
4.3.11. (1S*,5R*)-4,4-Dimethoxycarbonyl-1-hydroxy-2-
[(Z)-1-phenylethylidene]bicyclo[3.3.0]octane (3ea). IR
NMR d 1.96 (br s, 3H), 2.69 (s, 1H), 2.70 (d, J¼14.1 Hz,
1H), 2.77 (dd, J¼14.6, 1.7 Hz, 1H), 3.14 (dq, J¼17.3,
2.0 Hz, 1H), 3.60 (d, J¼17.4 Hz, 1H), 3.74 (s, 3H), 3.84
(Nujol) 3544, 1755, 1728, 1458, 1281, 1071 cmꢁ1 1H
;
NMR d 1.07–1.25 (m, 1H), 1.46–1.67 (m, 4H), 1.73–1.87

6138
T. Miura et al. / Tetrahedron 63 (2007) 6131–6140
(m, 1H), 1.96 (br s, 3H), 2.83–2.93 (m, 1H), 3.05 (d,
J¼17.4 Hz, 1H), 3.23 (s, 1H), 3.25 (dq, J¼17.3, 2.0 Hz,
1H), 3.74 (s, 3H), 3.80 (s, 3H), 7.16–7.39 (m, 5H); 13C
NMR d 23.7, 25.4, 29.4, 38.3, 41.9, 52.4, 53.1, 59.2, 59.6,
88.8, 126.4, 127.6, 128.2, 133.3, 139.8, 143.2, 170.6,
174.3; HRMS (FAB) calcd for C20H24O5 (M+) 344.1624,
found 344.1621.
140.5, 142.8, 145.5; HRMS (EI) calcd for C21H22O (M+)
290.1671, found 290.1670.
4.4.4. (2aS*,8bR*)-2a-Methyl-1-[(Z)-1-phenylpropyl-
idene]-2,2a,3,4-tetrahydro-1H-cyclobuta[a]naphthalen-
8b-ol (5da). IR (neat) 3443, 2963, 1601, 1456, 1175,
1
1107 cmꢁ1; H NMR d 0.84 (t, J¼7.7 Hz, 3H), 1.30 (s,
3H), 1.36 (td, J¼13.3, 4.6 Hz, 1H), 1.80 (ddd, J¼13.2, 4.4,
2.9 Hz, 1H), 2.02–2.26 (m, 3H), 2.43 (d, J¼15.6 Hz, 1H),
2.54 (d, J¼15.6 Hz, 1H), 2.70 (ddd, J¼15.6, 4.5, 2.7 Hz,
1H), 2.82 (ddd, J¼15.5, 13.1, 4.4 Hz, 1H), 6.67 (d, J¼
7.5 Hz, 1H), 6.77–6.86 (m, 1H), 6.90–6.98 (m, 2H), 6.98–
7.03 (m, 2H), 7.15–7.22 (m, 3H); 13C NMR d 12.4, 23.4, 27.4,
27.5, 32.1, 35.0, 40.7, 77.8, 125.5, 125.9, 126.4, 126.5, 127.2,
127.5, 128.7, 137.0, 138.6, 139.1, 139.7, 139.8; HRMS (EI)
calcd for C22H24O (M+) 304.1827, found 304.1828.
4.3.12. 3-Phenyl-4-[(Z)-1-phenylethylidene]tetrahydro-
furan-3-ol (3fa). IR (Nujol) 3436, 1493, 1204, 1100,
1
1038 cmꢁ1; H NMR d 1.97 (br s, 3H), 2.36 (br s, 1H),
3.85 (d, J¼9.0 Hz, 1H), 4.00 (d, J¼9.3 Hz, 1H), 4.74 (d,
J¼13.5 Hz, 1H), 4.89 (d, J¼13.5 Hz, 1H), 6.79–6.87 (m,
2H), 6.96–7.22 (m, 8H); 13C NMR d 22.7, 72.5, 81.1, 83.7,
125.2, 126.4, 126.7, 127.55, 127.60, 127.8, 131.5, 140.7,
141.0, 144.0; HRMS (FAB) calcd for C18H18O2 (M+)
266.1307, found 266.1307.
4.5. General procedure for the rhodium-catalyzed acyl
1,3-migration reaction
4.4. General procedure for arylative cyclization of
4-alkyn-1-ones 4
To an oven-dried, Ar-purged flask were added [Rh(OH)-
(cod)]2 (2.28 mg, 5 mmol, 5 mol % of Rh), arylboronic
acid 2 (2.0–5.0 equiv), and 1,4-dioxane (1 mL). A solution
of substrate 8 or 11 (0.20 mmol, 1.0 equiv) in 1,4-dioxane
(1.0 mL) and H2O (20 mL) was added to the reaction mixture
at room temperature. After complete consumption of the
substrate was observed, the reaction was quenched with aq
NH4Cl. Then, the resulting solution was stirred at room tem-
perature overnight. The aqueous layer was extracted with
ethyl acetate three times. The combined organic extracts
were washed with brine and dried over MgSO4. The solvent
was removed under reduced pressure and the residue was
purified by preparative thin layer chromatography (hexane/
ethyl acetate) to give the product 10 or 12. The ring-opening
of 11c, 11d, and 11f required three weeks for completion.
To an oven-dried, Ar-purged flask were added [Rh(OH)-
(cod)]2 (2.58 mg, 6.25 mmol, 5 mol % of Rh), arylboronic
acid 2 (1.25 mmol, 5.0 equiv), and 1,4-dioxane (1.25 mL).
A solution of substrate 4 (0.25 mmol, 1.0 equiv) in 1,4-diox-
ane (1.25 mL) and H2O (25 mL) was added to the reaction
mixture at room temperature. After complete consumption
of substrate was observed, water was added. The aqueous
layer was extracted with ethyl acetate three times. The com-
bined extracts were washed with brine and dried over
MgSO4. The solvent was removed under reduced pressure
and the residue was purified by preparative thin layer chro-
matography (hexane/ethyl acetate) to give the product 5.
4.4.1. 2,2-Dimethyl-1-phenyl-4-[(Z)-1-phenylpropyl-
idene]cyclobutan-1-ol (5aa). IR (neat) 3580, 2964, 1599,
1
1493, 1447, 1071 cmꢁ1; H NMR d 0.59 (s, 3H), 1.04 (t,
4.5.1. Ethyl 2-hydroxy-1-methyl-2-phenyl-3-[(Z)-1-phe-
nylethylidene]cyclobutane-1-carboxylate (9aa). This
compound is unstable. Only 1H NMR data are shown here:
1H NMR d 0.89 (t, J¼7.1 Hz, 3H), 1.48 (s, 3H), 2.09 (br s,
3H), 2.19 (s, 1H), 2.42 (dq, J¼15.8, 1.1 Hz, 1H), 3.36 (dq,
J¼15.6, 1.5 Hz, 1H), 3.49–3.70 (m, 2H), 7.12–7.63 (m,
10H).
J¼7.5 Hz, 3H), 1.23 (s, 3H), 1.85 (s, 1H), 2.31–2.55 (m,
4H), 7.06–7.17 (m, 5H), 7.22–7.29 (m, 1H), 7.30–7.38 (m,
2H), 7.40–7.46 (m, 2H); 13C NMR d 13.4, 24.1, 25.4, 26.4,
39.4, 41.5, 83.7, 126.6, 126.7, 127.6, 127.9, 128.1, 137.1,
139.2, 139.9, 144.7; HRMS (EI) calcd for C21H24O (M+)
292.1827, found 292.1833.
4.4.2. (1R*,6S*)-1-Hydroxy-6-methyl-8-[(Z)-1-phenyl-
ethylidene]bicyclo[4.2.0]octane (5ba). IR (Nujol) 3561,
4.5.2. Ethyl (Z)-4-benzoyl-2-methyl-5-phenylhex-4-
enoate (10aa). IR (neat) 2980, 1732, 1651, 1449, 1246,
1
1
3474, 2926, 1069 cmꢁ1; H NMR d 1.04 (s, 3H), 1.20–
1183 cmꢁ1; H NMR d 1.21 (t, J¼7.1 Hz, 3H), 1.25 (d,
1.66 (m, 7H), 1.81–1.88 (m, 2H), 1.91 (br s, 3H), 2.07 (d,
J¼14.1 Hz, 1H), 2.40 (d, J¼14.4 Hz, 1H), 7.18–7.25 (m,
1H), 7.26–7.36 (m, 4H); 13C NMR d 19.3, 21.0, 21.7, 23.4,
33.0, 35.5, 36.3, 39.1, 77.7, 126.6, 127.5, 127.8, 127.9,
141.5, 142.0; HRMS (EI) calcd for C17H22O (M+)
242.1671, found 242.1670.
J¼6.6 Hz, 3H), 2.26 (s, 3H), 2.59–2.77 (m, 2H), 2.92–3.05
(m, 1H), 4.06 (q, J¼7.1 Hz, 2H), 6.91–7.06 (m, 5H), 7.10–
7.18 (m, 2H), 7.22–7.29 (m, 1H), 7.57–7.63 (m, 2H); 13C
NMR d 14.2, 17.7, 20.9, 35.6, 38.9, 60.4, 127.3, 127.7,
127.8, 128.2, 129.2, 132.1, 135.2, 137.5, 141.3, 142.6,
176.1, 200.6; HRMS (CI) calcd for C22H25O3 (M+H+)
337.1804, found 337.1804.
4.4.3. (2aR*,7aS*)-7a-Methyl-2-[(Z)-1-phenylpropyl-
idene]-1,2,7,7a-tetrahydrocyclobuta[a]inden-2a-ol (5ca).
4.5.3. Ethyl (Z)-4-benzoyl-2-methyl-5-(4-fluorophenyl)-
hex-4-enoate (10ab). IR (neat) 2980, 1732, 1651, 1509,
1
IR (Nujol) 3467, 2961, 1601, 1456, 1144, 1069 cmꢁ1; H
1
NMR d 0.86 (t, J¼7.5 Hz, 3H), 1.31 (s, 3H), 2.02 (s, 1H),
2.14–2.24 (m, 3H), 2.48 (d, J¼15.3 Hz, 1H), 2.92 (d,
J¼16.5 Hz, 1H), 2.99 (d, J¼16.5 Hz, 1H), 6.95 (d,
J¼7.5 Hz, 1H), 7.10–7.25 (m, 3H), 7.30–7.46 (m, 5H); 13C
NMR d 12.6, 19.3, 27.3, 38.1, 45.0, 45.3, 89.0, 125.2,
125.3, 126.9, 127.0, 128.0, 128.2, 128.7, 136.5, 139.0,
1227, 1183 cmꢁ1; H NMR d 1.20 (t, J¼7.2 Hz, 3H), 1.24
(d, J¼6.6 Hz, 3H), 2.23 (s, 3H), 2.57–2.75 (m, 2H), 2.90–
3.03 (m, 1H), 4.06 (q, J¼7.1 Hz, 2H), 6.65–6.74 (m, 2H),
6.95–7.03 (m, 2H), 7.13–7.21 (m, 2H), 7.26–7.34 (m, 1H),
7.56–7.62 (m, 2H); 13C NMR d 14.1, 17.7, 20.9, 35.5,
38.8, 60.4, 114.7 (d, J¼20.9 Hz), 127.8, 129.1, 129.9

T. Miura et al. / Tetrahedron 63 (2007) 6131–6140
6139
1
(d, J¼8.1 Hz), 132.3, 135.6, 137.2, 138.5 (d, J¼3.5 Hz),
140.0, 161.7 (d, J¼247.1 Hz), 176.0, 200.5; HRMS (CI)
calcd for C22H24FO3 (M+H+) 355.1709, found 355.1708.
1664, 1449, 1250, 1183 cmꢁ1; H NMR d 0.20 (s, 9H),
1.17 (t, J¼7.1 Hz, 3H), 1.26 (d, J¼6.9 Hz, 3H), 2.49–2.63
(m, 1H), 2.79 (dd, J¼14.1, 7.5 Hz, 1H), 3.07 (dd, J¼14.4,
6.9 Hz, 1H), 3.97–4.08 (m, 2H), 6.72–6.79 (m, 2H), 6.84–
7.00 (m, 3H), 7.19–7.28 (m, 2H), 7.32–7.39 (m, 1H),
7.61–7.67 (m, 2H); 13C NMR d 0.7, 14.1, 17.7, 37.4, 38.3,
60.4, 125.6, 127.4, 127.9, 128.2, 129.1, 132.5, 136.6,
142.1, 145.6, 149.6, 175.7, 200.0; HRMS (CI) calcd for
C24H31O3Si (M+H+) 395.2042, found 395.2044.
4.5.4. Ethyl (Z)-4-benzoyl-2-methyl-5-(4-methylphenyl)-
hex-4-enoate (10ad). IR (neat) 2980, 1732, 1653, 1449,
1
1248, 1183 cmꢁ1; H NMR d 1.20 (t, J¼7.1 Hz, 3H), 1.24
(d, J¼6.9 Hz, 3H), 2.12 (s, 3H), 2.23 (s, 3H), 2.57–2.75 (m,
2H), 2.91–3.03 (m, 1H), 4.05 (q, J¼7.0 Hz, 2H), 6.81 (d,
J¼7.8 Hz, 2H), 6.88–6.96 (m, 2H), 7.12–7.20 (m, 2H), 7.23–
7.32 (m, 1H), 7.58–7.64 (m, 2H); 13C NMR d 14.1, 17.6, 20.9,
21.0, 35.6, 38.8, 60.4, 127.6, 128.1, 128.5, 129.2, 132.0,
134.7, 137.0, 137.4, 139.6, 141.3, 176.1, 200.8; HRMS
(CI) calcd for C23H27O3 (M+H+) 351.1960, found 351.1959.
4.5.10. Ethyl 4-oxo-3-[(Z)-1-phenylethylidene]cyclohep-
tane-1-carboxylate (12aa). IR (Nujol) 1725, 1648, 1289,
1161, 1102, 1028 cmꢁ1
;
1H NMR d 1.29 (t, J¼7.1 Hz,
3H), 1.63–1.86 (m, 2H), 1.92–2.09 (m, 1H), 2.10 (s, 3H),
2.16–2.52 (m, 4H), 2.54–2.67 (m, 1H), 2.97 (d, J¼
14.7 Hz, 1H), 4.18 (q, J¼6.9 Hz, 2H), 7.05–7.12 (m, 2H),
7.18–7.33 (m, 3H); 13C NMR d 14.2, 20.8, 22.5, 31.5,
32.6, 42.8, 45.3, 60.7, 126.97, 127.03, 128.1, 137.2, 140.0,
142.9, 174.8, 208.6; HRMS (EI) calcd for C18H22O3 (M+)
286.1569, found 286.1569.
4.5.5. Ethyl (Z)-4-benzoyl-2-methyl-5-(3-methoxyphe-
nyl)hex-4-enoate (10ae). IR (neat) 2980, 1730, 1656,
1578, 1221, 1179 cmꢁ1
;
1H NMR d 1.21 (t, J¼7.2 Hz,
3H), 1.25 (d, J¼6.6 Hz, 3H), 2.24 (s, 3H), 2.58–2.71 (m,
2H), 2.92–3.03 (m, 1H), 3.63 (s, 3H), 4.06 (q, J¼7.1 Hz,
2H), 6.50 (ddd, J¼8.2, 2.8, 1.0 Hz, 1H), 6.54–6.58 (m,
1H), 6.63 (ddd, J¼7.8, 1.5, 0.9 Hz, 1H), 6.92 (t, J¼7.8 Hz,
1H), 7.13–7.21 (m, 2H), 7.24–7.32 (m, 1H), 7.58–7.64 (m,
2H); 13C NMR d 14.1, 17.6, 20.7, 35.5, 38.8, 55.1, 60.4,
113.2, 113.6, 120.8, 127.6, 128.9, 129.0, 132.1, 135.2,
137.3, 141.0, 143.8, 158.8, 176.0, 200.6; HRMS (CI) calcd
for C23H27O4 (M+H+) 367.1909, found 367.1910.
4.5.11. Ethyl 9-oxo-8-[(Z)-1-phenylethylidene]-6,7,8,9-
tetrahydro-5H-benzo[7]annulene-6-carboxylate (12ba).
IR (Nujol) 1732, 1663, 1595, 1186, 1159 cmꢁ1; H NMR
1
d 1.30 (t, J¼7.2 Hz, 3H), 2.22 (s, 3H), 2.65 (dd, J¼14.7,
8.4 Hz, 1H), 2.95 (dd, J¼14.6, 7.4 Hz, 1H), 3.08–3.19 (m,
1H), 3.27–3.42 (m, 2H), 4.10–4.27 (m, 2H), 7.10–7.17 (m,
2H), 7.23–7.35 (m, 5H), 7.45 (td, J¼7.5, 1.5 Hz, 1H), 7.81
(dd, J¼7.8, 1.5 Hz, 1H); 13C NMR d 14.3, 22.5, 28.6,
33.9, 41.9, 60.9, 127.1, 127.4, 128.2, 129.7, 130.7, 132.7,
134.5, 137.4, 137.8, 143.7, 147.2, 173.8, 195.7; HRMS
(EI) calcd for C22H22O3 (M+) 334.1569, found 334.1567.
4.5.6. Ethyl (Z)-4-benzoyl-2-methyl-5-(3-chlorophenyl)-
hex-4-enoate (10af). IR (neat) 2980, 1732, 1653, 1449,
1
1242, 1183 cmꢁ1; H NMR d 1.18–1.27 (m, 6H), 2.23 (s,
3H), 2.58–2.76 (m, 2H), 2.92–3.03 (m, 1H), 4.07 (q,
J¼7.1 Hz, 2H), 6.86–6.94 (m, 3H), 6.99–7.03 (m, 1H),
7.14–7.22 (m, 2H), 7.25–7.34 (m, 1H), 7.54–7.62 (m, 2H);
13C NMR d 14.1, 17.7, 20.7, 35.5, 38.7, 60.5, 126.4, 127.3,
127.8, 128.2, 129.0, 129.1, 132.3, 133.6, 136.3, 137.2,
139.7, 144.2, 175.9, 200.2; HRMS (CI) calcd for
C22H24ClO3 (M+H+) 371.1414, found 371.1412.
4.5.12. Ethyl 4-oxo-3-[(Z)-1-phenylethylidene]cyclo-
octane-1-carboxylate (12ca). IR (neat) 2938, 1732, 1684,
1443, 1179, 1028 cmꢁ1
;
1H NMR d 1.27 (t, J¼7.2 Hz,
3H), 1.35–1.89 (m, 7H), 1.92–2.06 (m, 1H), 2.15 (s, 3H),
2.34–2.48 (m, 1H), 2.53–2.67 (m, 1H), 2.93 (dd, J¼13.8,
3.3 Hz, 1H), 4.14 (q, J¼7.1 Hz, 2H), 7.11–7.19 (m, 2H),
7.21–7.33 (m, 3H); 13C NMR d 14.3, 19.9, 24.4, 27.2,
29.7, 35.1, 43.1, 43.3, 60.6, 127.6, 127.7, 128.4, 135.8,
137.6, 142.5, 175.5, 215.4; HRMS (EI) calcd for
C19H24O3 (M+) 300.1725, found 300.1723.
4.5.7. Ethyl (Z)-4-benzoyl-2-methyl-5-phenylhept-4-
enoate (10ba). IR (neat) 2977, 1732, 1651, 1449, 1238,
1
1183 cmꢁ1; H NMR d 0.94 (t, J¼7.5 Hz, 3H), 1.22 (t,
J¼7.1 Hz, 3H), 1.25 (d, J¼6.6 Hz, 3H), 2.49–2.66 (m,
2H), 2.67–2.82 (m, 2H), 3.00 (dd, J¼14.1, 7.8 Hz, 1H),
4.07 (q, J¼7.1 Hz, 2H), 6.90–7.04 (m, 5H), 7.10–7.19 (m,
2H), 7.21–7.30 (m, 1H), 7.56–7.63 (m, 2H); 13C NMR
d 12.7, 14.1, 17.7, 27.2, 34.7, 38.8, 60.4, 127.2, 127.6,
127.7, 128.9, 129.1, 132.0, 134.5, 137.6, 140.8, 147.3, 176.0,
200.6; HRMS (CI) calcd for C23H27O3 (M+H+) 351.1960,
found 351.1959.
4.5.13. Ethyl 5,6,7,8,9,10-hexahydro-10-oxo-9-[(Z)-1-
phenylethylidene]benzo[8]annulene-7-carboxylate
(12da). IR (neat) 2936, 1732, 1653, 1445, 1240, 1184 cmꢁ1
;
1H NMR d 1.22 (t, J¼7.2 Hz, 3H), 2.00 (ddt, J¼13.7, 11.9,
4.6 Hz, 1H), 2.09–2.18 (m, 1H), 2.18–2.23 (m, 3H), 2.66
(tdd, J¼12.0, 4.1, 2.9 Hz, 1H), 2.80 (dd, J¼14.9, 12.2 Hz,
1H), 2.89–2.99 (m, 1H), 3.02 (dt, J¼14.4, 4.4 Hz, 1H),
3.65 (ddd, J¼14.3, 11.9, 4.0 Hz, 1H), 4.11 (q, J¼7.2 Hz,
2H), 6.96–7.05 (m, 2H), 7.08–7.23 (m, 5H), 7.40 (td,
J¼7.4, 1.5 Hz, 1H), 7.69 (dd, J¼7.7, 1.4 Hz, 1H); 13C
NMR d 14.2, 21.0, 31.8, 32.0, 32.1, 40.8, 60.7, 126.8,
126.9, 127.2, 128.0, 129.3, 131.3, 133.1, 136.2, 138.0,
138.9, 140.9, 142.7, 175.0, 199.8; HRMS (EI) calcd for
C23H24O3 (M+) 348.1725, found 348.1725.
4.5.8. Ethyl (Z)-4-acetyl-2-methyl-5-phenylhept-4-enoate
(10ca). IR (neat) 2979, 1732, 1676, 1352, 1177, 1121 cmꢁ1
;
1H NMR d 0.87 (t, J¼7.7 Hz, 3H), 1.19 (d, J¼6.6 Hz, 3H),
1.27 (t, J¼7.1 Hz, 3H), 1.58 (s, 3H), 2.36–2.69 (m, 4H),
2.78 (dd, J¼13.7, 8.6 Hz, 1H), 4.08–4.19 (m, 2H), 7.09–
7.15 (m, 2H), 7.28–7.34 (m, 3H); 13C NMR d 12.5, 14.3,
17.2, 27.9, 31.3, 34.2, 38.8, 60.4, 128.0, 128.4, 128.5,
138.0, 141.4, 148.0, 176.0, 207.3; HRMS (EI) calcd for
C18H24O3 (M+) 288.1725, found 288.1723.
4.5.14. Ethyl 4-oxo-3-[(Z)-1-phenylethylidene]cyclo-
decane-1-carboxylate (12ea). IR (neat) 2934, 1732, 1667,
1
4.5.9. Ethyl (E)-4-benzoyl-2-methyl-5-phenyl-5-tri-
methylsilylpent-4-enoate (10da). IR (neat) 2980, 1732,
1445, 1177, 1034 cmꢁ1; H NMR d 1.15–1.85 (m, 12H),
1.28 (t, J¼7.2 Hz, 3H), 2.16 (s, 3H), 2.60–2.78 (m, 2H),

6140
T. Miura et al. / Tetrahedron 63 (2007) 6131–6140
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2005, 127, 1094; (b) Miura, T.; Sasaki, T.; Nakazawa, H.;
Murakami, M. J. Am. Chem. Soc. 2005, 127, 1390; (c) Miura,
T.; Nakazawa, H.; Murakami, M. Chem. Commun. 2005,
2855; (d) Miura, T.; Murakami, M. Org. Lett. 2005, 7, 3339;
(e) Matsuda, T.; Makino, M.; Murakami, M. Angew. Chem.,
Int. Ed. 2005, 44, 4608; (f) Miura, T.; Sasaki, T.; Harumashi,
T.; Murakami, M. J. Am. Chem. Soc. 2006, 128, 2516; (g)
Shintani, R.; Tsurusaki, A.; Okamoto, K.; Hayashi, T. Angew.
Chem., Int. Ed. 2005, 44, 3909.
2.82–2.96 (m, 1H), 4.17 (q, J¼7.2 Hz, 2H), 7.11–7.20 (m,
2H), 7.26–7.35 (m, 3H); 13C NMR d 14.3, 21.7, 22.6, 24.5,
26.6, 30.1, 31.9, 42.4, 43.4, 60.5, 128.1, 128.4, 140.8,
142.2, 143.2, 176.1, 212.6; HRMS (EI) calcd for
C21H28O3 (M+) 328.2038, found 328.2039.
4.5.15. 5,9-Dioxo-6-methyl-8-[(Z)-1-phenylethylidene]-
6,7,8,9-tetrahydro-5H-benzo[7]annulene
(12fa).
IR
(neat) 2975, 1682, 1592, 1443, 1375, 1240 cmꢁ1; 1H NMR
d 1.31 (d, J¼6.6 Hz, 3H), 2.11 (s, 3H), 2.48 (dd, J¼14.9,
11.6 Hz, 1H), 2.88 (ddq, J¼15.3, 5.4, 0.9 Hz, 1H), 3.15–
3.30 (m, 1H), 6.91–6.98 (m, 2H), 7.17–7.25 (m, 3H),
7.51–7.66 (m, 3H), 7.68–7.72 (m, 1H); 13C NMR d 17.2,
21.5, 32.1, 45.8, 127.2, 128.1, 128.3, 128.4, 131.9, 132.3,
136.0, 137.8, 138.2, 142.4, 143.4, 197.0, 205.3; HRMS
(EI) calcd for C20H18O2 (M+) 290.1307, found 290.1306.
6. For aldehydes, see: (a) Sakai, M.; Ueda, M.; Miyaura, N.
€
Angew. Chem., Int. Ed. 1998, 37, 3279; (b) Furstner, A.;
Krause, H. Adv. Synth. Catal. 2001, 343, 343; (c) Pucheault,
^
M.; Darses, S.; Genet, J.-P. J. Am. Chem. Soc. 2004, 126,
15356; (d) Son, S. U.; Kim, S. B.; Reingold, J. A.; Carpenter,
G. B.; Sweigart, D. A. J. Am. Chem. Soc. 2005, 127, 12238;
(e) Suzuki, K.; Kondo, K.; Aoyama, T. Synthesis 2006, 1360;
For ketones, see: (f) Takezawa, A.; Yamaguchi, K.; Ohmura,
T.; Yamamoto, Y.; Miyaura, N. Synlett 2002, 1733; (g)
Shintani, R.; Inoue, M.; Hayashi, T. Angew. Chem., Int. Ed.
2006, 45, 3353; (h) Ueura, K.; Miyamura, S.; Satoh, T.;
Miura, M. J. Organomet. Chem. 2006, 691, 2821.
4.5.16. 2-Methyl-4-[(Z)-1-phenylethylidene]cyclooctane-
1,5-dione (12ga). IR (Nujol) 1700, 1671, 1306, 1125,
1
1073 cmꢁ1; H NMR d 1.12 (d, J¼6.3 Hz, 3H), 1.84–2.01
(m, 4H), 2.16 (s, 3H), 2.22–2.35 (m, 1H), 2.41–2.58 (m,
2H), 2.71 (dd, J¼13.4, 4.7 Hz, 1H), 2.93–3.07 (m, 1H),
7.12–7.19 (m, 2H), 7.25–7.33 (m, 3H); 13C NMR d 16.8,
19.8, 22.7, 38.4, 43.46, 43.51, 44.7, 127.7, 128.0, 128.5,
137.3, 138.1, 142.0, 213.0, 216.3; HRMS (EI) calcd for
C17H20O2 (M+) 256.1463, found 256.1464.
7. Preliminary communications of this work: (a) Miura, T.;
Shimada, M.; Murakami, M. Synlett 2005, 667; (b) Miura, T.;
Shimada, M.; Murakami, M. Angew. Chem., Int. Ed. 2005,
44, 7598; For a similar work, see also: (c) Shintani, R.;
Okamoto, K.; Otomaru, Y.; Ueyama, K.; Hayashi, T. J. Am.
Chem. Soc. 2005, 127, 54.
8. Hayashi, T.; Takahashi, M.; Takaya, Y.; Ogasawara, M. J. Am.
Chem. Soc. 2002, 124, 5052.
Acknowledgements
9. For regioselective 1,2-addition of arylboronic acids to alkynes,
see: (a) Lautens, M.; Yoshida, M. Org. Lett. 2002, 4, 123; (b)
This work was supported in part by a Grant-in-Aid for Young
Scientists (B) (No. 18750084) and Scientific Research on
Priority Areas (No. 18032040) from the Ministry of Edu-
cation, Culture, Sports, Science, and Technology, Japan.
M.S. acknowledges the Japan Society for the Promotion of
Science for the fellowship support.
^
Genin, E.; Michelet, V.; Genet, J.-P. Tetrahderon Lett. 2004,
45, 4157; (c) Genin, E.; Michelet, V.; Genet, J.-P.
^
J. Organomet. Chem. 2004, 689, 3820.
10. Shintani, R.; Okamoto, K.; Hayashi, T. Chem. Lett. 2005,
34, 1294.
11. For examples of photochemical acyl 1,3-migration of b,g-
unsaturated cyclic ketones, see: (a) Suginome, H.; Takemura,
M.; Shimoyama, N.; Orito, K. J. Chem. Soc., Perkin Trans. 1
1991, 2721; (b) Shin, J.; Fenical, W. J. Org. Chem. 1991,
56, 1227.
12. For examples of ring expansion through intramolecular
carbonyl addition/ring-opening, see: (a) Li, C.-J.; Chen,
D.-L.; Lu, Y.-Q.; Haberman, J. X.; Mague, J. T. J. Am. Chem.
Soc. 1996, 118, 4216; (b) Imai, A. E.; Sato, Y.; Nishida, M.;
Mori, M. J. Am. Chem. Soc. 1999, 121, 1217; (c) Tambar,
U. K.; Stoltz, B. M. J. Am. Chem. Soc. 2005, 127, 5340;
Review: (d) Wovkulich, P. M. Comprehensive Organic
Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford,
1991; Vol. 1, pp 892–897.
References and notes
ꢀ
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