Nickel-catalyzed acylstannylation and alkynylstannylation of 1,2-dienes

Article abstract of DOI:10.1016/j.jorganchem.2004.07.037

Carbostannylation of 1,2-dienes using acyl- and alkynylstannanes was achieved by means of nickel catalysis. In particular, acylstannylation of 1,2-dienes could be carried out with bis(1,5-cyclooctadiene)nickel [Ni(cod) ₂] and acylstannanes to give selectively α-acylmethyl(vinyl) stannanes. The reaction was also applicable to acylstannanes prepared in situ by protonolysis of α-alkoxyalkenylstannanes or by reactions of α-silyloxyvinylstannanes with aldehyde acetals. For alkynylstannylation, a combination of Ni(cod)₂ and 1,3-bis(diphenylphosphino)propane (dppp) was found to be effective to afford α-alkynylmethyl(vinyl)stannanes, whereas the Ni(cod)₂-1,3-bis(dimethylphosphino)propane (dmpp) catalyst switched the regioselectivity to give (Z)-α- alkynylmethyl(alkenyl)stannanes. The acylstannylation products were successfully converted into various conjugated or unconjugated enones by a combination of cross-coupling and NaH-catalyzed isomerization. The alkynylstannylation products were transformed by cross- or homo-coupling reactions to various enynes or 2,3-bis(alkynylmethyl)-1,3-dienes, versatile precursors for variously substituted polycyclic compounds.

Full text of DOI:10.1016/j.jorganchem.2004.07.037

Journal of Organometallic Chemistry 689 (2004) 3701–3721
www.elsevier.com/locate/jorganchem
Nickel-catalyzed acylstannylation and alkynylstannylation
of 1,2-dienes
a
b
a,
**
Yoshiaki Nakao , Eiji Shirakawa b,*,1, Teruhisa Tsuchimoto , Tamejiro Hiyama
a
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
b
Graduate School of Materials Science, Japan Advanced Institute of Science and Technology, Tatsunokuchi, Ishikawa 923-1292, Japan
Received 27 April 2004; accepted 22 July 2004
Available online 24 August 2004
Abstract
Carbostannylation of 1,2-dienes using acyl- and alkynylstannanes was achieved by means of nickel catalysis. In particular, acylst-
annylation of 1,2-dienes could be carried out with bis(1,5-cyclooctadiene)nickel [Ni(cod)2] and acylstannanes to give selectively
a-acylmethyl(vinyl)stannanes. The reaction was also applicable to acylstannanes prepared in situ by protonolysis of a-alkoxyalke-
nylstannanes or by reactions of a-silyloxyvinylstannanes with aldehyde acetals. For alkynylstannylation, a combination of Ni(cod)2
and 1,3-bis(diphenylphosphino)propane (dppp) was found to be effective to afford a-alkynylmethyl(vinyl)stannanes, whereas the
Ni(cod)2–1,3-bis(dimethylphosphino)propane (dmpp) catalyst switched the regioselectivity to give (Z)-a-alkynylmethyl(alke-
nyl)stannanes. The acylstannylation products were successfully converted into various conjugated or unconjugated enones by a
combination of cross-coupling and NaH-catalyzed isomerization. The alkynylstannylation products were transformed by cross-
or homo-coupling reactions to various enynes or 2,3-bis(alkynylmethyl)-1,3-dienes, versatile precursors for variously substituted
polycyclic compounds.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Nickel; Carbometalation; 1,2-diene; Acylstanane; Alkynylstannane
1. Introduction
alkoxyallenes or allenyl alcohols undergo carbometala-
tion with organomagnesiums [2], -zincs [3], -coppers
[4], and -indiums [5], whereas the reaction of allene with
allylmagnesium or -borane compounds is reported to
give cyclized products [6,7]. Very recently, allylmagnesi-
ation is shown to be applicable to a wide range of 1,2-
dienes [8]. Nevertheless, organometallics employed in
carbometalation of 1,2-dienes are limited to those hav-
ing a relatively polar carbon–metal bond. An alternative
strategy for carbometalation is three-component cou-
pling of inter-element compounds, 1,2-dienes and organic
halides, as demonstrated independently by Fleming and
Cheng [9], who prepared alkenyl- and/or allylsilanes, -
stannanes, -boranes and -germanes that tolerate a wide
variety of functional groups. During carbometalation,
however, one metal atom in the inter-element reagent
is lost.
Carbometalation reaction denotes an addition reac-
tion of nucleophilic organometallics across non-polar
unsaturated bonds and has been a powerful and valua-
ble synthetic tool, since the reaction allows simultaneous
formation of both carbon–carbon and carbon–metal
bonds in a single step [1]. Although alkynes and alkenes
have been extensively studied for carbometalation, 1,2-
dienes have remained yet to be explored. Indeed,
*
Corresponding authors. Tel.: +81 75 753 3985; fax: +81 75 753
3988 (E. Shirakawa), **Tel.: +81 75 383 2446; fax: +81 75 383 2445
(T. Hiyama).
E-mail addresses: shirakawa@kuchem.kyoto-u.ac.jp (E. Shira-
kawa), thiyama@npc05.kuic.kyoto-u.ac.jp (T. Hiyama).
1
Present address: Department of Chemistry, Graduate School of
Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan.
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.07.037

3702
Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
Direct carbostannylation of unsaturated bonds
oxyphenylallene (2d) and phenylallene (2e) gave the ben-
zoylstannylation products 3e and 3f in comparable
yields and selectivities (entries 4 and 5), whereas that
of 4-trifluoromethylphenylallene (2f) gave 3g in a low
yield (entry 6). Methoxyallene (2g) afforded the corre-
sponding product 3h exclusively albeit in a low yield (en-
try 7). Tributyl(propanoyl)tin (1c) also reacted with a
series of 1,2-dienes successfully (entries 8–11), while
the reaction of carbamoylstannane (1d) with allene af-
forded only a 25% yield of 3m even under harsh condi-
tions (entry 12). Although the minor isomer(s) could not
be characterized thoroughly in these cases, 119Sn NMR
peak(s) observed at ꢀ42.2 to 14.2 ppm were attributed
to an alkenyl- or allyl(trialkyl)stannane.
should be of significant synthetic value from the view-
point of atom economy. In addition, the resulting
organostannanes are compatible with a wide variety of
functional groups and are easily purified prior to subse-
quent transformations such as the Migita–Kosugi–Stille
coupling reaction [10]. We have disclosed that carbost-
annylation of alkynes and 1,3-dienes catalyzed by a pal-
ladium or nickel catalyst provides efficient access to
variously functionalized alkenyl- and allylstannanes
[11,12]. Accordingly, we envisaged that 1,2-dienes would
also undergo the carbostannylation. This was found to
be the case [13], as reported herein in detail.
Ni(cod)2
O
SnR2
3
O
(5 mol%)
toluene
•
2. Results and discussions
+
(2)
R1
R3
R1
SnR2
3
R3
2.1. Acylstannylation of 1,2-dienes
1a: R1 = Ph, R2 = Me
1b: R1 = Ph, R2 = Bu
1c: R1 = Et, R2 = Bu
2a: R3 = Bu
3
2b: R3 = H
2c: R3 = t-Bu
We first examined the reaction of benzoyl(tri-
methyl)tin (1a) with 1,2-heptadiene (2a) in the presence
of Ni(cod)2 (5 mol%) in toluene at 50 ꢁC, the standard
conditions for the acylstannylation of alkynes and 1,3-
dienes [11b,12] (Eq. (1)), and obtained 3-benzoyl-2-
trimethylstannyl-1-heptene (3a) in 79% yield together
with (E)-1-phenyl-3-trimethylstannyl-3-octen-1-one (4)
(4% yield) and 2-methylene-1-phenyl-3-trimethylstan-
nylheptan-1-one (5) (5% yield). Use of a ligand like
PPh3, 1,3-bis(diphenylphosphino)propane (dppp), pyri-
dine, or 2,2ꢀ-bipyridyl or of a polar solvent like THF,
1,4-dioxane, or DMF resulted in predominant forma-
tion of trimethyl(phenyl)stannane, a decarbonylated
product of 1a, as was the case with 1,3-diene-acylstanny-
lation [12].
1d: R1 = (CH2)5N, R2 = Me 2d: R3 = 4-MeO-C6H4
2e: R3 = Ph
2f: R3 = 4-CF3-C6H4
2g: R3 = MeO
Disubstituted allenes also participated in the present
reaction. Acylstannanes 1a or 1c reacted with 3-me-
thyl-1,2-butadiene (2h) highly regioselectively to give
3n or 3o, respectively (Eq. (3)), while those with 4,5-non-
adiene (2i) afforded a mixture of stereoisomers (Eq. (4)).
Ni(cod)2
(5 mol%)
O
SnR2
3
O
+
(3)
•
R1
R1
SnR2
3
toluene
2h
1a: R1 = Ph, R2 = Me
1c: R1 = Et, R2 = Bu
temp. time
yield (3:isomers)
50 ˚C 6 h
80 ˚C 5 h
3n: R1 = Ph, R2 = Me
3o: R1 = Et, R2 = Bu
63% (>99:1)
49% (83:17)
O
Ni(cod)2 (5 mol%)
50 ˚C, 1.5 h
•
+
Bu
Ph
SnMe3
Ni(cod)2
O
SnR2
3
1a
2a
Pr
O
(5 mol%)
+
(4)
•
2i
R1
R1
SnR2
3
toluene, 2 h
Pr
O
Ph
ð1Þ
O
SnMe3
Me3Sn
Bu
O
Pr
Pr
1a: R1 = Ph, R2 = Me
1c: R1 = Et, R2 = Bu
+
+
Me3Sn
Ph
Ph
temp.
yield (3:isomers) E :Z
Bu
3a (79%)
50 ˚C 3p: R1 = Ph, R2 = Me 72% (>99:1)
80 ˚C 3q: R1 = Et, R2 = Bu 54% (81:19)
63:37
56:44
Bu
5 (5%)
4 (4%)
The scope of the present reaction was examined next
as summarized in Eq. (2) and Table 1. Benzoylstannyla-
tion of allene (2b) also proceeded under its atmosphere
to give the benzoylstannylation product 3b in 64% yield
together with (E)-1-phenyl-3-trimethylstannyl-2-buten-
1-one (2%), an isomerized product of 3b (entry 1). Reac-
tion of benzoyl(tributyl)tin (1b) proceeded in a similar
way albeit in a lower yield and selectivity (entry 2). A
bulky diene, 4,4-dimethyl-1,2-pentadiene (2c), under-
went benzoylstannylation with similar regioselectivity
(entry 3). The reaction is also applicable to arylallenes
of different electronic nature. Thus, reactions of 4-meth-
2.2. In situ preparation of acylstannanes
2.2.1. One-pot hydrolysis–acylstannylation
Although acylstannanes are readily available by the
reported procedures [14], some of them are air-sensitive
and thus are hard to deal with. To improve the utility of
the acylstannylation reaction, we examined in situ prep-
aration of acylstannanes from their stable precursors. It
is reported that a-(alkoxy)alkenylstannanes, readily
available by lithiation of the corresponding enol ethers
followed by reaction with stannyl halides [15], are

Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
3703
Table 1
Nickel-catalyzed acylstannylation of 1,2-dienesa
3:isomersc
Yield of 3 (%)b
1,2-Diene
Entry
Acylstannane
Major product
Time (h)
1d
2d
1a
1b
2b
2b
R = Me (3b)
R = Bu (3c)
1.5
4
64
48
97:3e
79:21
O
SnR3
Ph
Ph
O
SnMe3
3
1a
2c
3d
1.5
59
86:14
t-Bu
O
SnMe3
4
5
6
1a
1a
1a
2d
2e
2f
R = OMe (3e)
R = H (3f)
2
2
2
50
53
35
78:22
77:23
66:34
Ph
R = CF3 (3g)
R
O
O
SnMe3
7
1a
2g
3h
2
26
97:3
Ph
Et
OMe
SnBu3
8f
9d,f
10f
1c
1c
1c
2a
2b
2e
3i
2
53
67
43
89:11
94:6
Bu
O
O
SnBu3
SnBu3
3j
3k
1.5
3.5
Et
Et
79:21
Ph
O
SnBu3
f
2.5
2
48
25
11
1c
2g
2b
3l
95:5
Et
OMe
O
SnMe3
h
12d,g
1d
3m
—
N
a
The reaction was carried out unless otherwise stated in toluene (0.4 ml) at 50 ꢁC using an acylstannane (0.30 mmol), a 1,2-diene (0.90 mmol), and
Ni(cod)2 (15 lmol).
Isolated yields based on the acylstannane.
b
c
Determined by 119Sn NMR.
d
The reaction was carried out under an allene atmosphere (1 atm).
(E)-1-Phenyl-3-trimethylstannyl-2-buten-1-one (2%) was obtained.
e
f
The reaction was carried out at 80 ꢁC.
The reaction was carried out at 100 ꢁC in the presence of 60 lmol of Ni(cod)2.
Accompanied by a complex mixture of products other than 3m.
g
h

3704
Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
convertible into acylstannanes upon hydrolysis [16].
Thus, we took this approach and then the resulting
acylstannanes were used for reaction with 1,2-dienes.
Hydrolysis of 1-ethoxyvinyl(trimethyl)tin (6a) with a
1 M aqueous hydrochloric acid solution in diethyl ether
at room temperature for 1 h [16], followed by neutraliza-
tion with K2CO3, gave acetyl(trimethyl)tin, which was,
without isolation, treated with 2a and a toluene solution
of Ni(cod)2 (5 mol%) at 50 ꢁC for 3 h to give the acylst-
annylation product 7a in 63% yield (Scheme 1 and entry
1 of Table 2). Similar operations were applied to reac-
tions of tributyl(1-ethoxyvinyl)tin (6b), a tributylstannyl
analog of 6a, and 1-ethoxy-1-propenylstannane (6c),
giving the corresponding acylstannylation products 7b
and 7c (entries 2 and 3). The present one-pot hydroly-
sis–acylstannylation was also applicable to 1-methoxy-
1,3-butadienylstannane (6d), which was reported to give
(E)-2-butenoylstannane stereoselectively upon hydroly-
sis [15a], affording the corresponding enoylstannylation
product 7d albeit in a modest yield (entry 4).
2.2.2. One-pot aldol condensation–acylstannylation
Another precursor of acylstannanes is a-(silyl-
oxy)vinylstannane (8) that is readily prepared [17] and
derivatized [18]. We first examined the reaction of 8 with
benzaldehyde dimethylacetal (9a) in the presence of tri-
methylsilyl trifluoromethanesulfonate (Me3SiOTf) [19]
and confirmed the formation of cinnamoylstannane
10a in 90% yield by 119Sn NMR (Eq. (5)). No trace of
simple aldol adduct 11 was detected in a crude product
mixture. Use of a less amount of Me3SiOTf reduced the
yield of 10a. Although 11 could be formed also with
BF3 Æ Et2O as a Lewis acid instead of Me3SiOTf, the
sample of 11 thus prepared failed to participate in the
acylstannylation. In any case, these results encouraged
us to study one-pot aldol condensation–acylstannyla-
tion reaction.
OSiMe3
SnBu3
O
OMe
OMe
a–c
+
(5)
one-pot
O
Ph
SnBu3
Ph
OEt(Me)
SnR2
K2CO3
1 M HCl aq.
solvent, rt
R1
R
SnR2
3
10a (90% by 119Sn NMR)
9a
8
3
6a: R1 = H, R2 = Me
6b: R1 = H, R2 = Bu
6c: R1 = Me, R2 = Me
(E:Z = 38:62)
6d: R1 = vinyl, R2 = Me
(E:Z = >99:1)
Reagents and conditions: (a) Me3SiOTf (2.5 equiv),CH2Cl2, –78 ˚C,1h
SnR2
3
2a
O
(b) sat. NaHCO3 aq., –40 ˚C to rt (c) K2CO3
Ni(cod)2 (5 mol%)
R
toluene, 50 ˚C, 3 h
OMe
O
Bu
7
Ph
SnBu3
11
Scheme 1.
Table 2
One-pot hydrolysis–acylstannylation of 1,2-heptadiene
Entry
Alkenylstannane
Solvent
Time (h)b
Product
Yield (%)c
7:isomer(s)d
O
SnR2
3
1
6a
6b
Et2O
THF
R2 = Me (7a)
R2 = Bu (7b)
63
81
97:3
92:8
1
1
2e
Bu
O
SnMe3
3
6c
Et2O
THF
3
7c
61
41
98:2
93:7
Et
Bu
O
SnMe3
4f
6.5
7d
6d
Bu
a
Hydrolysis was carried out in THF or diethyl ether (0.1 ml) and a 1 M aqueous HCl solution (10 ll) using an a-(alkoxy)alkenylstannane (0.2
mmol). Acylstannylation was carried out in toluene (0.5 ml) using 1,2-heptadiene (0.6 mmol) and Ni(cod)2 (10 lmol) at 50 ꢁC.
For hydrolysis.
b
c
Isolated yields based on 6.
Determined by 119Sn NMR.
d
e
Acylstannylation was carried out at 80 ꢁC for 1 h.
Before addition of Ni(cod)2 and 1,2-heptadiene, THF was evaporated.
f

Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
3705
At first, 10a prepared as above was treated with 2a
and 5 mol% of a Ni(cod)2 catalyst in toluene at room
temperature for 1 h to give the acylstannylation product
12a in 51% yield (Scheme 2 and entry 1 of Table 3). Nei-
ther electron-donating nor -withdrawing substituents on
the aromatic aldehyde acetals interfered in the reaction,
giving acylstannylation products 12b–12d (entries 2–4)
in moderate yields. However, the reaction of an aliphatic
aldehyde acetal 9e afforded the expected product 12e in
a low yield (entry 5).
2.3. Alkynylstannylation of 1,2-dienes
We next studied alkynylstannylation of 1,2-dienes
using trimethyl(phenylethynyl)tin (13a) and 2a under
the conditions for acylstannylation. As all attempts
failed to give the desired product selectively, we screened
various ligands to find that bidentate bisphoshpine
ligands to form a six-membered chelate to nickel
played a crucial role. Use of dppp gave a mixture of
alkynylstannylation products, 5-phenyl-2-trimethylstan-
nyl-1-penten-4-yne (14a) and (Z)-1-phenyl-4-trimethyl-
OSiMe3
SnBu3
O
OMe
Me3SiOTf
+
CH2Cl2, –78 ˚C
R
SnBu3
R
OMe
9a: R = Ph
8
10
9b: R = 4-Me-C6H4
9c: R = 4-Cl-C6H4
9d: R = 4-MeO2C-C6H4
9e: R = Et
stannyl-4-nonen-1-yne (15a) (85:15) in
a
72%
2a
O
SnBu3
Ni(cod)2 (5 mol%)
combined yield (Eq. (6) and entry 1 of Table 4). Ligands
for five- or seven-membered chelate retarded the reac-
tion. Further study on the substituent effect led to the
observation that a dialkylphosphorus analog of dppp re-
versed the regioselectivity. For example, 1,3-bis(dime-
R
toluene, rt
Bu
12
Scheme 2.
Table 3
One-pot aldol condensation–acylstannylation of 1,2-heptadiene
Yield of 12 (%)c
Entry
Aldehyde acetal
Product
Time (h)b
12:isomer(s)d
O
SnBu3
1
9a
12a
1
51
>99:1
Bu
O
O
SnBu3
2
3
9b
9c
12b
12c
1
5
49
54
95:5
Bu
SnBu3
Me
Cl
>99:1
Bu
O
SnBu3
4
9d
9e
12d
12e
5
1
42
95:5
Bu
MeO2C
Et
O
SnBu3
5e
12f
89:11
Bu
a
Aldol condensation was carried out in CH2Cl2 (0.5 ml) using tributyl[1-(trimethylsilyloxy)vinyl]tin (0.20 mmol), an aldehyde acetal (0.22 mmol),
and TMSOTf (0.5 mmol) at ꢀ78 ꢁC. Acylstannylation was carried out in toluene (0.5 ml) using 1,2-heptadiene (0.6 mmol) and Ni(cod)2 (10 lmol) at rt.
b
Time for acylstannylation.
Isolated yields based on 8.
c
d
Determined by 119Sn NMR.
e
Aldol condensation was carried out at ꢀ40 ꢁC.
f
Determined by 119Sn NMR using tetrabutyltin as an internal standard.

3706
Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
Table 4
Nickel-catalyzed alkynylstannylation of 1,2-dienesa
Yield (%)b
Temp. (˚C)
Products
14:15c
1,2-diene
Entry Ligand Alkynylstannane
Time (h)
Ph
SnMe3
SnMe3
Ph
1
2
2a
2ad
dppp
13a
13a
50
50
10
10
72
82
85:15
32:68
Bu
dmpp
Bu
14a
15a
Ph
SnMe3
3e
dppp
13a
2b
30
10
63
–
14b
Ph
Ph
SnMe3
SnMe3
Ph
Ph
4
5
dppp
2c
2cd
50
50
70
49
57
67
98:2
13a
13a
t-Bu
dmpp
14:86
t-Bu
14c
15c
SnMe3
SnMe3
6
dppp
2g
0
23
53
28:72
13a
MeO
OMe
14d
15d
Ph
Ar
SnBu3
SnBu3
Ph
7
8
dppp
13b
13b
2a
2ad
60
60
40
46
70
70f
87:13
37:63
Bu
Bu
dmpp
Bu
14e
15e
SnMe3
SnMe3
Ar
9
dppp
dppp
13c
30
30
5
92
52
87:13
77:23
2a
2a
10
13d
72
Bu
Ar = 4-CF3-C6H4: 14f
Ar = 4-CF3-C6H4: 15f
Ar = 4-MeO-C6H4: 14g Ar = 4-MeO-C6H4: 15g
Me3Si
SnMe3
SnMe3
11e
12e
dppp
dppp
dmpp
50
50
60
7
24
46
91
–
–
13e
13f
13e
2b
2b
14h
14i
Et3Si
90
Me3Si
SnMe3
f
2ad
37:63
SnMe3
SiMe3 81
13
Bu
Bu
14j
15j
a
The reaction was carried out in toluene (0.3 ml) at 50 ꢁC using an alkynylstannane (0.20 mmol), a 1,2-diene (0.60 mmol), Ni(cod)2 (10 lmol), and
a ligand (10 lmol).
b
Combined isolated yields of 14 and 15 based on the alkynylstannane.
Determined by 119Sn NMR.
1,2-Diene (0.30 mmol) was used.
c
d
e
f
The reaction was carried out under an allene atmosphere.
Determined by 119Sn NMR using Bu4Sn (entry 8) or Me4Sn (entry 13) as an internal standard.

Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
3707
Ph
thylphosphino)propane (dmpp) gave a mixture of 14a
+
•
and 15a in 32:68 (entry 2). We next examined the scope
and limitation of the reaction. Allene (2b) also promoted
the reaction (entry 3). A bulky 1,2-diene, 4,4-dimethyl-
1,2-pentadiene (2c), reacted with 13a with highly con-
trasting regiochemistry by the two catalysts (entries 4
and 5). It is worthy to note that the addition of 13a
across methoxyallene (2g) proceeded mainly at the ter-
minal double bond at 0 ꢁC even under the Ni–dppp
catalysis (entry 6). We also studied the scope of alkynyl-
stannanes. Tributylstannyl analog 13b reacted with 1,2-
heptadiene (2a) in a manner similar to 13a (entries 7 and
8). An electron-withdrawing 4-CF3 group on the phenyl
in 13a increased both reaction rate and yield, presuma-
bly due to enhanced reactivity at the oxidative addition
step (vide infra, entry 9), while an electron-donating 4-
MeO group behaved in an opposite manner (entry 10).
(Trialkylsilyl)ethynylstannanes, 13e and 13f, also partic-
ipated in the reaction with allene and 1,2-heptadiene,
giving a-[(silylethynyl)methyl]vinylstannanes in good
yields (entries 11–13).
SnMe3
13a
2h
Ni(cod)2 (5 mol%)
dppp (5 mol%)
Ph
SnMe3
SnMe3
Ph
+
(7)
toluene, 50 ˚C, 60 h
96:4
37%
14k
15k
Ph
SnMe3
Pr
Ni(cod)2 (5 mol%)
dppp (5 mol%)
Ph
Pr
•
+
SnMe3
toluene, 50 ˚C, 17 h
ð8Þ
Pr
Pr
14l
69%
13a
2i
2.4. Reaction mechanism
A plausible mechanism of the carbostannylation of
1,2-dienes is summarized in Scheme 3. Based on the
previous observations [11,20], we may reasonably as-
sume that the reaction is initiated by the oxidative
addition of a C–Sn bond of organostannanes to a
Ni(0) complex. Oxidative adduct 16 is coordinated by
a 1,2-diene at the less hindered double bond to avoid
steric bulk around the nickel center as depicted in 17
rather than 18. The Sn group on Ni then migrates to
the cumulative carbon to give r-allylnickel complex
19, which should isomerize to anti-p-allylnickel inter-
mediate 20. Reductive elimination of the R1 and R2-
substituted carbon that is cis to R1 gives product 22
as was observed in the acylstannylation and alkynylst-
annylation with Ni–dppp catalyst [21]. The electron-
withdrawing nature of an acyl moiety might facilitate
reductive elimination from 20 to give 22 with rather
higher regioselectivities than alkynylstannylation.
R1
SnR2
3
Ni(cod)2 (5 mol%)
ligand (5 mol%)
•
R1
SnR2
3
+
(6)
R3
toluene
R3
13
2
14
13a: R1 = Ph, R2 = Me
13b: R1 = Ph, R2 = Bu
2a: R3 = Bu
2b: R3 = H
13c: R1 = 4-CF3-C6H4, R2 = Me
2c: R3 = t-Bu
SnR2
R1
3
13d: R1 = 4-MeO-C6H4, R2 = Me 2g: R3 = MeO
13e: R1 = Me3Si R2 = Me
R3
+
13f: R1 = Et3Si R2 = Me
15
Disubstituted allenes also reacted with 13a in the
presence of Ni–dppp catalyst. For example, the reaction
with 2h gave less substituted vinylstannane 14k selec-
tively albeit in a low yield (Eq. (7)). The alkynylstanny-
lation of 2i afforded the (Z)-alkenylstannane 14l
exclusively (Eq. (8)).
R1–Sn
L–Ni(0)
Sn
R2
R3
R2
R3
R1
L =
L
R1 Sn
Ni
dmpp
Ni
R2
25
R3
Sn
Sn
R1
–Ni(0)
R1
L
16
R2
R1 = acyl or alkynyl
•
– Ni(0)
Sn
23
21
R2
R3
R3
R2
≥
R1 Sn
Ni
R1 Sn
Ni
L
Ni
R2
L =
none or
dppp
R1
Carbo-
nickelation
R1
R2
Ni
R2
L
•
R1
•
Sn
Sn
R2
24
R3
L
R3
or
–Ni(0)
R3
R3
20
17
18
R3
Stannyl-
nickelation
R1
L
22
Sn
R2
Ni
R3
19
Scheme 3.

3708
Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
In the alkynylstannylation with Ni–dmpp, it is rea-
forded (Z)-b-arylenone 30. Thus, both stereoisomers 28
and 30 were prepared selectively starting with 3j simply
by changing the order of operation. Stereoselective
isomerization of 3j to 29 might be attributed to an intra-
molecular interaction between the oxygen and tin atoms
in 29 [12,22]. Cross-coupling reaction of 3j with benzoyl
chloride proceeded similarly to give enedione 31. a-
Dimethylation of 3j gave 3o, which also cross-coupled
with 26 to afford 32.
sonable to assume that the electron-donative nature of
dmpp might retard reductive elimination to allow 20
to isomerize to thermodynamically more stable syn-p-
allylnickel complex 21, whose R1 is positioned cis to
the less hindered allyl. Subsequent reductive elimination
should give (Z)-alkenylstannane 23. Migratory insertion
of a 1,2-diene into the Ni–C bond via 18 seems unlikely,
because this should lead to (E)-alkenylstannane
25 through (E)-alkenylnickel intermediate 24 followed
by stereo-retained reductive elimination,
a
route
2.5.2. Transformation of alkynylstannylation products
The synthetic utility of the alkynylstannylation
inconsistent with the experimental observations: both
acylstannylation and alkynylstannylation afford (Z)-
alkeny- lstannanes or its mixture with (E)-isomers as
shown in Eqs. (4) and (8).
products is demonstrated with 14b as
a model
(Scheme 5) [23]. Palladium-catalyzed cross-coupling
reaction of 14b with iodobenzene, vinyl bromide, or
1-bromo-2-phenylethyne successfully gave various
kinds of the alkynylmethyl substituted conjugated
p-system.
2.5. Synthetic potential of carbostannylation products
2.5.1. Transformation of acylstannylation products
In addition to the cross-coupling reaction, oxidative
homo-coupling reaction is another versatile transforma-
tion of the alkynylstannylation products (Eq. (9)). For
example, oxidative homo-coupling [24] of 14a with a
palladium catalyst and a stoichiometric amount of
CuCl/CuCl2 afforded 2,3-disubstituted 1,3-butadiene
36a as a mixture of dl and meso isomers in an almost
1:1 ratio but in a high yield. The diastereoisomerism is
not present in the reaction of 14b and 14i, and the cor-
responding 2,3-bis(alkynylmethyl)-1,3-butadienes 36b
and 36c were obtained in good yields.
The synthetic utility of acylstannylation products is
obvious. With 3j as a model, typical transformations
are demonstrated in Scheme 4. Cross-coupling reaction
of 3j with ethyl 4-iodobenzoate (26) using a Pd2(dba)3
catalyst gave coupled product 27 in 91% yield without
cine-substitution. Conjugation of 27 leading to (E)-b-
arylenone 28 was performed with NaH. In contrast,
the olefin isomerization can be carried out at first. Con-
jugation of 3j with NaH gave (Z)-alkenylstannane 29
exclusively; subsequent cross-coupling of 29 with 26 af-
CO2Et
O
a
b
O
91%
65%
28
CO2Et
27
29
O
SnBu3
CO2Et
3j
O
SnBu3
O
b
c
88%
69%
30
d
O
3j
3j
O
83%
CO2Et
31
O
SnBu3
O
e
a
58%
73%
3o
32
Scheme 4. Reagents and conditions: (a) 4-EtO2C-C6H4-I (26, 1.0 equiv), 2.5 mol% of Pd2(dba)3, NMP, 30 ꢁC, 15 h (from 3j to 27) or 10 h (from 3o to
32); (b) NaH (0.2 equiv), THF, rt, 4 h (from 3j to 29) or 3 h (from 27 to 28); (c) 26 (1.0 equiv), 5 mol% of Pd2(dba)3, NMP, 30 ꢁC, 69 h; (d) PhCOCl
(1.0 equiv), 2.5 mol% of Pd2(dba)3, NMP, 30 ꢁC, 8 h; (e) Me–I (3.0 equiv), NaH (3.0 equiv), THF, rt, 17 h.

Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
3709
The versatility of dienediynes 36 as synthetic precur-
sors of polycyclic compounds is demonstrated in
Scheme 6. Desilylation of 36c with TBAF gave 36d
[25], which underwent two different modes of cycliza-
tion either at a conjugated 1,3-diene or 1,6-diyne moi-
ety. Thus, annulation through the Diels–Alder
reaction with diethyl acetylenedicarboxylate followed
by nickel-catalyzed acetylene trimerization gave 38, a
tetrahydroanthracene framework [26]. Similarly, the
Diels–Alder reaction of dienediyne 36a or 36b gave
37a or 37b, respectively. The diyne moiety in 37b was
further transformed by zirconocene-mediated reaction
with o-diiodobenzene to give 39 having a tetrahydro-
tetracene skeleton [27]. Alternatively, 36b was first trea-
ted with a zirconium complex to afford tetraene 40,
which underwent double Diels–Alder reaction with
diethyl acetylenedicarboxylate to give hexahydroan-
thracene 41. Thus, variously functionalized polyacene
structures that are gaining growing interest in material
chemistry [28] are available by the synthetic scheme de-
scribed herein.
I
Ph
Ph
(1.0 equiv)
a, 87%
33
34
Br
Ph
SnMe3
(3.0 equiv)
b, 47%
14b
Ph
Br
Ph
(1.3 equiv)
c, 83%
Ph
35
Scheme 5. Reagents and conditions: (a) Pd(PPh3)4 (5 mol%), LiCl (1.5
equiv), CuCl (1.0 equiv), DMSO, 50 ꢁC, 4.5 h; (b) Pd2(dba)3 (2.6
mol%), LiCl (1.5 equiv), CuCl (1.0 equiv), DMSO–THF, 50 ꢁC, 19 h;
(c) Pd(PPh3)4 (5 mol%), LiCl (1.5 equiv), CuCl (1.0 equiv), DMSO, 50
ꢁC, 4 h.
R2
Pd(PPh3)4 (5 mol%)
CuCl (1.0 equiv)
CuCl2 (1.0 equiv)
R1
SnMe3
R1
R1
(9)
3. Conclusion
DMSO
R2
14
R2
In conclusion, we have demonstrated nickel-catalyzed
acyl- and alkynylstannylation of 1,2-dienes and their
synthetic potential for variously conjugated p-systems
as well as linearly fused hydropolyacenes through
cross-coupling and homo-coupling reactions followed
36
R1
R2
Bu (14a) 50 ˚C 3 h
temp. time product yield
Ph
Ph
Et3Si
36a
36b
82% (dl:meso = ca. 1:1)
H
H
(14b) 50 ˚C 2 h
86%
73%
(14h) 40 ˚C 0.8 h 36c
R2
36a: R1 = Ph, R2 = Bu
36b: R1 = Ph, R2 = H
R1
R1
36c: R1 = Et3Si, R2 = H
a, 92%
36d: R1 = R2 = H
R2
b
e
55%
R2
Ph
R1
R1
CO2Et
37a: R1 = Ph, R2 = Bu (89%)
37b: R1 = Ph, R2 = H (84%)
CO2Et 37c: R1 = R2 = H (100%)
R2
Ph
40
c
d
f
70%
56%
CO2Et
40%
Ph
Ph
Ph
CO2Et EtO2C
CO2Et EtO2C
CO2Et
CO2Et
CO2Et
Ph
38
39
41
Scheme 6. Reagents and conditions: (a) Bu4NF (4.0 equiv), AcOH (5.2 equiv), THF, rt, 44 h, 92%; (b) EtO2CC ” CCO2Et (5.0 equiv), toluene, 100 ꢁC,
37 h (from 36a to 37a); 28 h (from 36b to 37b); 23 h (from 36d to 37c); (c) Ni(acac)2 (30 mol%), (i-Bu)2AlH (60 mol%), PPh3 (1.2 equiv), HC ” CH (1
atm), THF, rt, 21 h; (d) Cp2ZrBu2 (1.7 equiv), THF, ꢀ78 ꢁC, 1 h then rt, 1 h, then o-I2C6H4 (3.0 equiv), CuCl (3.9 equiv), N,N0-
dimethylpropyleneurea (5.1 equiv), 50 ꢁC, 15 h; (e) Cp2ZrBu2 (2.0 equiv), THF, ꢀ78 ꢁC, 1 h then rt, 1 h, then CuCl (4.3 equiv), N,N0-
dimethylpropyleneurea (6.0 equiv), rt, 2 h; (f) EtO2CC ” CCO2Et (8.0 equiv), toluene, 100 ꢁC, 28 h.

3710
Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
by annulation via cycloadditions. Acylstannylation
selectively affords a-acylmethyl(vinyl)stannanes,
whereas alkynylstannylation gives either of the regioiso-
was stirred at the temperature shown in Table 1, Eqs. (3)
and (4). After the time specified in Table 1, Eqs. (3) and
(4), the reaction mixture was filtered through a Florisil
pad. The filtrate was concentrated and purified by pre-
parative GPC. Yields are listed in Table 1, Eqs. (3)
and (4).
mers stereoselectively by proper choice of a ligand.
4. Experimental
4.2.1. 2-Butyl-1-phenyl-3-trimethylstannyl-3-buten-1-one
(3a)
4.1. General remarks
A colorless oil, Rf 0.52 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.15 (s, 9H), 0.88 (t,
J = 7.0 Hz, 3H), 1.12–1.61 (m, 5H), 1.74–1.95 (m, 1H),
4.22 (t, J = 7.0 Hz, 1H), 5.35 (d, J = 2.2 Hz, 1H), 5.82
(dd, J = 2.2, 0.7 Hz, 1H), 7.34–7.58 (m, 3H), 7.66–8.05
(m, 2H); 13C NMR (75.5 MHz, CDCl3) d ꢀ8.1, 13.8,
22.5, 29.6, 32.6, 58.6, 128.1, 128.5, 128.6, 133.0, 137.1,
155.2, 202.2; 119Sn{1H} NMR (149 MHz, CDCl3) d
ꢀ31.7; IR (neat): 2957, 2930, 2858, 1676, 1597, 1580,
1448, 1344, 1221, 1200, 1180, 1003, 922, 841, 772, 733,
712, 694, 667, 529 cmꢀ1; HRMS (ESI) Calc. for
C17H26O120SnNa: M+ + Na, 389.0903. Found: m/z
389.0896.
All manipulations of oxygen- and moisture-sensitive
materials were conducted with a standard Schlenk
technique under an argon or nitrogen atmosphere. Nu-
clear magnetic resonance spectra were taken on a Var-
ian INOVA 500 (1H, 500 MHz; 13C, 126 MHz; 119Sn,
186 MHz), Varian INOVA 400 (1H, 400 MHz; 13C,
101 MHz; 119Sn, 149 MHz), Varian Gemini 2000
(1H, 300 MHz; 13C, 75.5 MHz), JEOL EX-270 (1H,
270 MHz; 13C, 67.8 MHz; 119Sn, 101 MHz), or Varian
Mercury 200 (1H, 200 MHz; 13C, 50 MHz) spectrom-
eter using tetramethylsilane (1H and 13C) as an internal
standard or tetramethyltin (119Sn) as an external stand-
ard. Infrared spectra were recorded on a Shimadzu
FTIR-8400 spectrometer. Preparative recycling gel per-
meation chromatography (GPC), preparative recycling
reversed phase chromatography, or preparative recy-
cling silica gel chromatography were performed with
a JAI LC-908 chromatograph equipped with JAI-
GEL-1H and 2H (chloroform as an eluent), JAI-
GEL-ODS (acetonitrile–THF as an eluent), or
JAIGEL-SIL (hexane–ethyl acetate as an eluent) col-
umn, respectively. High-resolution mass spectra
(HRMS) were obtained with a JEOL JMS-700 (EI),
JEOL JMS-HX110A (FAB+), or Bruker Bio APEX
70e (ESI) spectrometer. Unless otherwise noted, rea-
gents were commercially available and used without
further purification. Toluene and THF were distilled
from sodium/benzophenone ketyl. Dichloromethane
was distilled from phosphorus pentoxide. Anhydrous
NMP and DMSO were purchased from Aldrich and
used as received. Bis(1,5-cyclooctadiene)nickel, pur-
chased from Kanto Chemicals, was recrystallized from
toluene/1,5-cyclooctadiene (50:1). Acylstannanes [14],
a-alkoxyalkenylstannanes [15], tributyl[1-(trimethylsi-
lyloxy)vinyl]tin [17], alkynylstannanes [29], 1,2-dienes
[30], and 1,3-bis(dimethylphosphino)propane [31] were
prepared according to the corresponding literature
procedure.
4.2.2. (E)-1-Phenyl-3-trimethylstannyl-3-nonen-1-one (4)
A colorless oil, Rf 0.53 (hexane–ethyl acetate = 9:1).
1H NMR (500 MHz, CDCl3) d 0.09 (s, 9H), 0.87–0.97
(m, 3H), 1.18–1.48 (m, 4H), 2.17 (q, J = 6.9 Hz, 2H),
3.99 (d, J = 1.8 Hz, 2H), 5.79 (tt, J = 6.9, 1.8 Hz,
JSn–H = 76.0 Hz, 1H), 7.43–7.61 (m, 3H), 7.93–8.02
(m, 2H); 119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ29.4;
HRMS (ESI) Calc. for C17H26O120SnNa: M+ + Na,
389.0903. Found: m/z 389.0914.
4.2.3. 2-Methylene-1-phenyl-3-trimethylstannyl-1-hepta-
none (5)
A colorless oil, Rf 0.56 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.09 (s, 9H), 0.90 (t,
J = 7.0 Hz, 3H), 1.17–1.84 (m, 6H), 2.42 (t, J = 8.1
Hz, 1H), 5.39 (s, 1H), 5.61 (s, 1H), 7.38–7.57 (m, 3H),
7.70–7.76 (m, 2H); 119Sn{1H} NMR (149 MHz, CDCl3)
d 10.0; HRMS (ESI) Calc. for C17H26O120SnNa:
M+ + Na, 389.0903. Found: m/z 389.0896.
4.2.4. 2-tert-Butyl-1-phenyl-3-trimethylstannyl-3-buten-1-
one (3d)
A colorless oil, Rf 0.57 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.14 (s, 9H), 0.99 (s,
9H), 4.20 (s, 1H), 5.53 (d, J = 2.1 Hz, 1H), 5.87 (d,
J = 2.1 Hz, 1H), 7.36–7.63 (m, 3H), 7.83–8.02 (m, 2H);
13C NMR (75.5 MHz, CDCl3) d ꢀ7.0, 28.5, 35.4, 65.5,
128.3, 128.6, 131.4, 132.8, 139.0, 153.2, 203.4;
119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ27.5; HRMS
(ESI) Calc. for C17H26O120SnNa: M+ + Na, 389.0903.
Found: m/z 389.0896.
4.2. A general procedure for acylstannylation of 1,2-
dienes
To a stirred solution of an acylstannane (0.30 mmol)
and Ni(cod)2 (4.1 mg, 15 lmol) in toluene (0.4 ml), 1,2-
diene (0.90 mmol) was added, and the resulting mixture

Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
3711
4.2.5. 2-(4-Methoxyphenyl)-1-phenyl-3-trimethylstannyl-
3-buten-1-one (3e)
119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ42.5; HRMS
(ESI) Calc. for C22H44O120SnNa: M+ + Na, 467.2310.
Found: m/z 467.2331.
A colorless oil, Rf 0.26 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.06 (s, 9H), 3.77 (s,
3H), 5.43 (t, J = 1.1 Hz, 1H), 5.47 (s, 1H), 5.65 (t,
J = 1.5 Hz, 1H), 6.84 (dt, J = 8.8, 2.1 Hz, 2H), 7.12
(dt, J = 8.8, 2.1 Hz, 2H), 7.31–7.57 (m, 3H), 7.87–8.04
(m, 2H); 13C NMR (75.5 MHz, CDCl3) d ꢀ8.4, 55.1,
61.7, 114.1, 127.1, 128.6, 128.8, 130.2, 130.4, 133.0,
136.9, 155.4, 158.7, 200.2; 119Sn{1H} NMR (149 MHz,
4.2.10. 4-Phenyl-5-tributylstannyl-5-hexen-3-one (3k)
A colorless oil, Rf 0.57 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.64–1.48 (m, 30H),
2.50 (q, J = 7.4 Hz, 2H), 4.65 (s, 1H), 5.37 (t, J = 1.6
Hz, 1H), 5.60 (t, J = 1.6 Hz, 1H), 7.01–7.42 (m, 5H);
13C NMR (75.5 MHz, CDCl3) d 7.8, 10.2, 13.6, 27.3,
28.8, 36.1, 67.0, 127.16, 127.20, 128.5, 129.2, 137.9,
153.6, 210.6; 119Sn{1H} NMR (149 MHz, CDCl3) d
ꢀ38.1; HRMS (ESI) Calc. for C24H40O120SnNa:
M+ + Na, 487.1997. Found: m/z 487.2011.
120
CDCl3) d ꢀ28.3; HRMS (ESI) Calc. for C20H24O2
SnNa: M+ + Na, 439.0695. Found: m/z 439.0696.
4.2.6. 1,2-Diphenyl-3-trimethylstannyl-3-buten-1-one (3f)
A colorless oil, Rf 0.39 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.05 (s, 9H), 5.45 (t,
J = 1.5 Hz, 1H), 5.52 (s, 1H), 5.68 (t, J = 1.5 Hz, 1H),
7.15–7.58 (m, 8H), 7.87–8.02 (m, 2H); 13C NMR (75.5
MHz, CDCl3) d ꢀ8.4, 62.5, 127.2, 127.5, 128.6, 128.7,
128.9, 129.1, 133.1, 136.9, 138.5, 155.2, 200.0;
119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ27.6; HRMS
(ESI) Calc. for C19H22O120SnNa: M+ + Na, 409.0589.
Found: m/z 409.0603.
4.2.11. 4-Methoxy-5-tributylstannyl-5-hexen-3-one (3l)
A colorless oil, Rf 0.46 (hexane–ethyl acetate = 9:1).
1H NMR (200 MHz, CDCl3) d 0.73–1.71 (m, 30H),
2.48 (qd, J = 7.3, 1.2 Hz, 2H), 3.31 (s, 3H), 4.18 (t,
J = 1.8 Hz, 1H), 5.41 (t, J = 1.8 Hz, 1H), 5.87 (t,
J = 1.8 Hz, 1H); 13C NMR (126 MHz, CDCl3) d 7.3,
10.2, 13.7, 27.3, 29.0, 30.4, 57.2, 93.3, 127.0, 152.4,
210.5; 119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ40.6;
HRMS (ESI) Calc. for C19H38O2120SnNa: M+ + Na,
441.1789. Found: m/z 441.1792.
4.2.7. 1-Phenyl-2-(4-trifluoromethylphenyl)-3-trimethyl-
stannyl-3-buten-1-one (3g)
A colorless oil, Rf 0.34 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.06 (s, 9H), 5.50 (t,
J = 1.1 Hz, 1H), 5.59 (s, 1H), 5.69 (t, J = 1.4 Hz, 1H),
7.24–7.68 (m, 7H), 7.85–8.06 (m, 2H); 13C NMR (75.5
MHz, CDCl3) d ꢀ8.5, 62.0, 125.6 (q, J = 3.5 Hz),
128.4, 128.8, 128.9, 129.5 (q, J = 36.9 Hz), 129.6,
133.4, 136.6, 142.4, 154.2, 199.2; 119Sn{1H} NMR (149
MHz, CDCl3) d ꢀ24.4; HRMS (ESI) Calc. for
C20H21F3O120SnNa: M+ + Na, 477.0463. Found: m/z
477.0467.
4.2.12. 2,2-Dimethyl-1-phenyl-3-trimethylstannyl-3-buten-
1-one (3n)
A colorless oil, Rf 0.49 (hexane–ethyl acetate = 9:1).
1H NMR (200 MHz, CDCl3) d 0.11 (s, 9H), 1.39 (s,
6H), 5.40 (d, J = 1.0 Hz, 1H), 5.85 (d, J = 1.0 Hz, 1H),
7.26–7.58 (m, 3H), 7.74–8.03 (m, 2H); 13C NMR (67.8
MHz, CDCl3) d ꢀ7.8, 27.4, 55.0, 124.0, 127.8, 129.9,
131.8, 136.6, 161.1, 204.5; 119Sn{1H} NMR (149 MHz,
CDCl3) d ꢀ27.6; Anal. Calc. for C15H22OSn: C, 53.45;
H, 6.58. Found: C, 53.71; H, 6.53%.
4.2.8. 2-Methoxy-1-phenyl-3-trimethylstannyl-3-buten-1-
one (3h)
4.2.13. 4,4-Dimethyl-5-tributylstannyl-5-hexen-3-one (3o)
A colorless oil, Rf 0.57 (hexane–ethyl acetate = 10:1).
1H NMR (300 MHz, CDCl3) d 0.76–1.56 (m, 30H), 1.22
(s, 6H), 2.40 (q, J = 7.1 Hz, 2H), 5.28 (t, J = 1.1 Hz, 1H),
5.72 (t, J = 1.1 Hz, 1H); 13C NMR (75.5 MHz, CDCl3) d
8.1, 10.7, 13.5, 25.1, 27.3, 28.9, 30.5, 55.4, 124.7, 160.0,
214.6; 119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ38.3;
HRMS (ESI) Calc. for C20H40O120SnNa: M+ + Na,
439.1997. Found: m/z 439.2006.
A colorless oil, Rf 0.32 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.18 (s, 9H), 3.35 (s,
3H), 4.94 (t, J = 1.9 Hz, 1H), 5.47 (t, J = 1.6 Hz, 1H),
5.84 (t, J = 1.6 Hz, 1H), 7.31–7.61 (m, 3H), 7.89–8.10
(m, 2H); 13C NMR (75.5 MHz, CDCl3) d ꢀ8.6, 57.1,
91.3, 127.4, 128.4, 129.5, 133.2, 135.0, 153.1, 199.1;
119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ27.8; HRMS
(ESI) Calc. for C14H20O120SnNa: M+ + Na, 363.0383.
Found: m/z 363.0373.
4.2.14. (E)-1-Phenyl-2-propyl-3-trimethylstannyl-3-hep-
ten-1-one [(E)-3p]
4.2.9. 4-Butyl-5-tributylstannyl-5-hexen-3-one (3i)
A colorless oil, Rf 0.61 (hexane–ethyl acetate = 10:1).
1H NMR (300 MHz, CDCl3) d 0.77–1.80 (m, 39H),
2.21–2.61 (m, 2H), 3.25 (t, J = 7.1 Hz, 1H), 5.26 (d,
J = 2.2 Hz, 1H), 5.75 (d, J = 2.2 Hz, 1H); 13C NMR
(75.5 MHz, CDCl3) d 7.5, 10.2, 13.6, 13.8, 22.5, 27.3,
28.9, 29.7, 31.3, 35.2, 64.0, 128.2, 154.5, 212.6;
A colorless oil, Rf 0.58 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.06 (s, 9H), 0.79–0.99
(m, 6H), 1.17–1.55 (m, 5H), 1.80–1.95 (m, 1H), 2.27
(q, J = 6.6 Hz, 2H), 4.67 (t, J = 7.0 Hz, 1H), 5.69 (td,
J = 6.6, 0.8 Hz, JSn–H = 76.1 Hz, 1H), 7.38–7.58 (m,

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Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
3H), 7.90–7.97 (m, 2H); 13C NMR (75.5 MHz, CDCl3) d
ꢀ7.7, 13.9, 14.1, 20.5, 22.6, 31.3, 35.2, 50.5, 128.4, 128.5,
132.9, 137.5, 142.6, 144.1, 203.2; 119Sn{1H} NMR (149
MHz, CDCl3) d ꢀ29.1; HRMS (ESI) Calc. for
C19H30O120SnNa: M+ + Na, 417.1216. Found: m/z
417.1207.
4.3.1. 1-Phenyl-3-trimethylstannyl-3-buten-1-one (3b)
A colorless oil, Rf 0.39 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.16 (s, 9H), 3.98 (t,
J = 1.4 Hz, 2H), 5.40 (dt, J = 1.6, 1.4 Hz, 1H), 5.82
(dt, J = 1.6, 1.4 Hz, 1H), 7.42–7.61 (m, 3H), 7.94–8.01
(m, 2H); 13C NMR (75.5 MHz, CDCl3) d ꢀ8.8, 49.6,
128.3, 128.4, 128.7, 133.2, 136.8, 149.6, 199.5;
119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ34.3; HRMS
(ESI) Calc. for C13H18O120SnNa: M+ + Na, 333.0277.
Found: m/z 333.0260.
4.2.15. (Z)-1-Phenyl-2-propyl-3-trimethylstannyl-3-hep-
ten-1-one [(Z)-3p]
A colorless oil, Rf 0.56 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.20 (s, 9H), 0.80 (t,
J = 7.3 Hz, 3H), 0.92 (t, J = 7.1 Hz, 3H), 1.17–1.54
(m, 5H), 1.76–1.93 (m, 1H), 1.98 (q, J = 7.1 Hz, 2H),
4.3.2. 1-Phenyl-3-tributylstannyl-3-buten-1-one (3c)
A colorless oil, Rf 0.57 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.74–1.04 (m, 15H),
1.18–1.67 (m, 12H), 3.93 (t, J = 1.4 Hz, 2H), 5.36 (dt,
J = 1.6, 1.4 Hz, 1H), 5.82 (dt, J = 1.6, 1.4 Hz, 1H),
7.41–7.61 (m, 3H), 7.91–8.02 (m, 2H); 13C NMR (75.5
MHz, CDCl3) d 10.0, 13.6, 27.3, 29.0, 50.3, 128.4,
128.6, 128.8, 133.1, 136.9, 149.0, 199.4; 119Sn{1H}
NMR (149 MHz, CDCl3) d ꢀ42.9; HRMS (ESI) Calc.
for C22H36O120SnNa: M+ + Na, 459.1684. Found: m/z
459.1686.
4.00 (t, J = 6.9 Hz, 1H), 5.97 (t, J = 7.1 Hz, J119Sn–H
=
139.8 Hz, 1H), 7.34–7.57 (m, 3H), 7.78–7.97 (m, 2H);
13C NMR (75.5 MHz, CDCl3) d ꢀ7.1, 13.4, 14.0, 20.9,
22.8, 34.7, 36.3, 56.7, 128.4, 128.5, 132.5, 137.3, 142.9,
143.7, 202.1; 119Sn{1H} NMR (149 MHz, CDCl3) d
ꢀ47.8; HRMS (ESI) Calc. for C19H30O120SnNa:
M+ + Na, 417.1216. Found: m/z 417.1207.
4.2.16.
[(E)-3q]
(E)-4-Propyl-5-tributylstannyl-5-nonen-3-one
4.3.3. 5-Tributylstannyl-5-hexen-3-one (3j)
A colorless oil, Rf 0.63 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.71–1.80 (m, 42H),
2.20 (q, J = 6.9 Hz, 2H), 2.24–2.56 (m, 2H), 3.75 (t,
J = 6.7 Hz, 1H), 5.67 (t, J = 6.9 Hz, J Sn–H = 66.8 Hz,
1H); 13C NMR (75.5 MHz, CDCl3) d 7.5, 10.5, 13.6,
13.8, 14.0, 20.4, 22.8, 27.3, 29.0, 31.9, 33.7, 35.1, 55.4,
143.4, 143.7, 213.0; 119Sn{1H} NMR (149 MHz, CDCl3)
d ꢀ40.1; HRMS (ESI) Calc. for C24H48O120SnNa:
M+ + Na, 495.2622. Found: m/z 495.2622.
A colorless oil, Rf 0.60 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.76–1.13 (m, 18H),
1.17–1.61 (m, 12H), 2.43 (q, J = 7.4 Hz, 2H), 3.34 (s,
2H), 5.28 (dt, J = 1.6, 0.8 Hz, 1H), 5.73 (dt, J = 1.6,
0.8 Hz, 1H); 13C NMR (75.5 MHz, CDCl3) d 7.7, 9.9,
13.6, 27.3, 28.8, 28.9, 35.4, 128.7, 148.7, 210.4;
119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ43.7; HRMS
(ESI) Calc. for C18H36O120SnNa: M+ + Na, 411.1684.
Found: m/z 411.1680.
4.3.4. N-(3-Trimethylstannyl-3-butenoyl)piperidine (3m)
A colorless oil, Rf 0.46 (hexane–ethyl acetate = 2:1).
1H NMR (300 MHz, CDCl3) d 0.14 (s, 9H), 1.40–1.75
(m, 6H), 3.30 (t, J = 1.6 Hz, 2H), 3.32–3.40 (m, 2H),
3.47–3.58 (m, 2H), 5.31 (dt, J = 2.4, 1.6 Hz, 1H), 5.71
(dt, J = 2.4, 1.6 Hz, 1H); 13C NMR (75.5 MHz, CDCl3)
d ꢀ8.8, 24.4, 25.5, 26.3, 42.6, 44.8, 46.7, 126.6, 150.3,
170.0; 119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ31.9;
HRMS (ESI) Calc. for C12H23NO120SnNa: M+ + Na,
340.0699. Found: m/z 340.0681.
4.2.17.
[(Z)-3q]
(Z)-4-Propyl-5-tributylstannyl-5-nonen-3-one
A colorless oil, Rf 0.66 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.88–1.79 (m, 42H),
1.99 (q, J = 7.1 Hz, 2H), 2.15–2.54 (m, 2H), 3.13 (t,
J = 6.6 Hz, 1H), 5.99 (t, J = 7.1 Hz, JSn–H = 128.6 Hz,
1H); 13C NMR (75.5 MHz, CDCl3) d 7.9, 10.9, 13.6,
13.7, 14.0, 20.9, 23.0, 27.3, 29.1, 33.6, 35.1, 36.8, 61.6,
142.0, 143.9, 213.0; 119Sn{1H} NMR (149 MHz, CDCl3)
d ꢀ40.1; HRMS (ESI) Calc. for C24H48O120SnNa:
M+ + Na, 495.2622. Found: m/z 495.2622.
4.4. A general procedure for one-pot hydrolysis–acylstan-
nylation of 1,2-dienes
4.3. A general procedure for acylstannylation of allene
To a solution of an a-alkoxyvinylstannane (0.20
mmol) in THF or Et2O (0.10 ml), 1 M HCl aqueous
solution (25 ll, 25 lmol) was added, and the resulting
mixture was stirred at room temperature. After the time
specified in Table 2, the mixture was treated with solid
K2CO3 (14 mg, 0.10 mmol), and a solution of Ni(cod)2
(2.8 mg, 10 lmol) in toluene (0.5 ml) and 1,2-heptadiene
(58 mg, 0.60 mmol) were added successively. The result-
Allene was bubbled into a solution of an acylstann-
ane (0.30 mmol) and Ni(cod)2 (4.1 mg, 15 lmol) in tol-
uene (0.4 ml) for 10 min at the temperature specified in
Table 1. The reaction mixture was stirred for the time
specified in Table 1 and filtered through a Florisil pad.
The filtrate was concentrated and purified by prepara-
tive GPC. Yields are listed in Table 1.

Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
3713
ing mixture was stirred at 50 ꢁC for 3 h and filtered
through a Florisil pad. The filtrate was concentrated
and purified by preparative GPC to give an acylstanny-
lation product. Yields are listed in Table 2.
(34 mg, 0.22 mmol) in CH2Cl2 (0.5 ml) was added
TMSOTf (111 mg, 0.5 mmol) at ꢀ78 ꢁC, and the result-
ing mixture was stirred for 1 h at ꢀ78 ꢁC before a satu-
rated Na2CO3 aqueous solution (50 ll) was added at
ꢀ40 ꢁC. The mixture was allowed to warm to room tem-
perature and treated with solid K2CO3 (69 mg, 0.50
mmol). Solvents were evaporated in vacuo, and the res-
idue was dissolved in CDCl3 (0.5 ml). To the solution
was added Bu4Sn (76 mg, 0.22 mmol) as an internal
standard. 1H and 119Sn NMR showed the following
peaks which was ascribed to (E)-tributyl(cinnam-
4.4.1. 3-Butyl-4-trimethylstannyl-4-penten-2-one (7a)
A colorless oil, Rf 0.34 (hexane–ethyl acetate = 10:1).
1H NMR (270 MHz, CDCl3) d 0.14 (s, 9H), 0.87 (t,
J = 7.0 Hz, 3H), 1.08–1.45 (m, 5H), 1.63–1.82 (m, 1H),
2.10 (s, 3H), 3.27 (t, J = 7.1 Hz, 1H), 5.36 (d, J = 2.4
Hz, 1H), 5.78 (dd, J = 2.4, 0.1 Hz, 1H); 13C NMR
(50.0 MHz, CDCl3) d ꢀ8.2, 13.9, 22.5, 29.2, 29.5, 30.9,
64.8, 128.3, 154.3, 210.1; 119Sn{1H} NMR (101 MHz,
1
oyl)stannane (10a) [32] (90% yield by 119Sn NMR). H
NMR (200 MHz, CDCl3) d 6.71 (d, J = 15.0 Hz, 1H),
7.28 (d, J = 15.0 Hz, 1H), 7.38–7.64 (m, 5H) (multiplets
in d 0.65–1.90, including peaks of Bu4Sn, were also obse-
reved); 119Sn NMR (101 MHz, CDCl3) d ꢀ89.6.
CDCl3)
C12H24O120Sn: M+, 289.0614. Found: m/z 289.0616.
d
ꢀ31.3; HRMS (FAB+) Calc. for
4.4.2. 3-Butyl-4-tributylstannyl-4-penten-2-one (7b)
A colorless oil, Rf 0.57 (hexane–ethyl acetate = 10:1).
1H NMR (200 MHz, CDCl3) d 0.72–1.85 (m, 36H), 2.10
(s, 3H), 3.24 (t, J = 7.0 Hz, 1H), 5.32 (d, J = 2.2 Hz, 1H),
5.79 (dd, J = 2.2, 0.9 Hz, 1H); 13C NMR (50.0 MHz,
CDCl3) d 10.3, 13.6, 13.9, 22.6, 27.4, 29.0, 29.2, 29.8,
30.9, 64.7, 128.4, 153.9, 209.7; 119Sn{1H} NMR (101
MHz, CDCl3) d ꢀ41.8; HRMS (FAB+) Calc. for
4.6. A general procedure for one-pot aldol condensation–
acylstannylation of 1,2-dienes
To a solution of tributyl[1-(trimethylsilyloxy)vinyl]tin
(81 mg, 0.20 mmol) and an aldehyde acetal (0.22 mmol)
in CH2Cl2 (0.5 ml) was added TMSOTf (111 mg, 0.5
mmol) at ꢀ78 ꢁC, and the resulting mixture was stirred
for 1 h at ꢀ78 ꢁC before saturated Na2CO3 aqueous solu-
tion (50 ll) was added at ꢀ40 ꢁC. The mixture was allowed
to warm to room temperature and treated with solid
K2CO3 (69 mg, 0.50 mmol). To the mixture were added
a solution of Ni(cod)2 (2.8 mg, 10 lmol) in toluene (0.5
ml) and 1,2-heptadiene (58 mg, 0.60 mmol), and the whole
mixture was stirred at room temperature for the time spec-
ified in Table 3 before filtration through a Florisil pad.
The filtrate was concentrated, the residue was purified
by preparative GPC to give acylstannylation products
in yields listed in Table 3.
C17H33O120Sn: M+
373.1556.
– Bu, 373.1553. Found: m/z
4.4.3. 4-Butyl-5-trimethylstannyl-5-hexen-3-one (7c)
A colorless oil, Rf 0.60 (hexane–ethyl acetate = 10:1).
1H NMR (200 MHz, CDCl3) d 0.13 (s, 9H), 0.78–1.48
(m, 11H), 1.60–1.82 (m, 1H), 2.26–2.61 (m, 2H), 3.28
(t, J = 7.2 Hz, 1H), 5.31 (d, J = 2.2 Hz, 1H), 5.75 (dd,
J = 2.2, 0.7 Hz, 1H); 13C NMR (50.0 MHz, CDCl3) d
ꢀ8.2, 7.6, 14.0, 22.5, 29.6, 31.4, 35.3, 64.1, 127.9,
154.8, 212.8; 119Sn{1H} NMR (101 MHz, CDCl3) d
ꢀ32.7; HRMS (EI) Calc. for C12H23O120Sn: M+ – Me,
303.0771. Found: m/z 303.0769.
4.6.1. (E)-4-Butyl-1-phenyl-5-tributylstannyl-1,5-hexa-
dien-3-one (12a)
4.4.4.
one (7d)
(E)-3-Butyl-2-trimethylstannyl-1,5-heptadien-4-
A colorless oil, Rf 0.56 (hexane–ethyl acetate = 10:1).
1H NMR (200 MHz, CDCl3) d 0.74–1.08 (m, 18H),
1.14–1.59 (m, 17H), 1.77–1.96 (m, 1H), 3.51 (t, J = 7.0
Hz, 1H), 5.35 (d, J = 2.4 Hz, 1H), 5.86 (dd, J = 2.4,
0.8 Hz, 1H), 6.79 (d, J = 15.9 Hz, 1H), 7.32–7.43 (m,
3H), 7.48–7.64 (m, 3H); 13C NMR (67.8 MHz, CDCl3)
d 10.5, 13.8, 14.1, 22.8, 27.5, 29.1, 29.9, 31.3, 63.1,
125.5, 128.2, 128.6, 128.8, 130.2, 134.7, 141.9, 153.8,
200.2; 119Sn{1H} NMR (101 MHz, CDCl3) d ꢀ41.6;
HRMS (FAB+) Calc. for C24H37O120Sn: M+ – Bu,
461.1866. Found: m/z 461.1861.
A colorless oil, Rf 0.50 (hexane–ethyl acetate = 10:1).
1H NMR (200 MHz, CDCl3) d 0.12 (s, 9H), 1.01–1.95
(m, 9H), 1.87 (dd, J = 6.8, 1.6 Hz, 3H), 3.45 (t, J = 7.1
Hz, 1H), 5.33 (d, J = 2.6 Hz, 1H), 5.75 (dd, J = 2.4,
0.8 Hz, 1H), 6.15 (dq, J = 15.6, 1.6 Hz, 1H), 6.87 (dq,
J = 15.6, 6.8 Hz, 1H); 13C NMR (125 MHz, CDCl3) d
ꢀ8.0, 13.9, 18.2, 22.5, 29.6, 31.5, 61.9, 127.8, 131.1,
142.5, 154.7, 200.9; 119Sn{1H} NMR (101 MHz, CDCl3)
d ꢀ32.9; HRMS (EI) Calc. for C13H23O120Sn: M+ – Me,
315.0771. Found: m/z 315.0774.
4.6.2. (E)-4-Butyl-1-(4-methylphenyl)-5-tributylstannyl-
1,5-hexadien-3-one (12b)
A colorless oil, Rf 0.60 (hexane–ethyl acetate = 10:1).
1H NMR (200 MHz, CDCl3) d 0.73–1.09 (m, 18H),
1.15–1.68 (m, 17H), 1.75–1.97 (m, 1H), 2.37 (s, 3H),
3.51 (t, J = 7.0 Hz, 1H), 5.34 (d, J = 2.2 Hz, 1H), 5.85
4.5. Reaction of tributyl[1-(trimethylsilyloxy)vinyl]tin
with benzaldehyde dimethyl acetal
To a solution of tributyl[1-(trimethylsilyloxy)vinyl]tin
(81 mg, 0.20 mmol) and benzaldehyde dimethyl acetal

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Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
(dd, J = 2.2, 0.7 Hz, 1H), 6.74 (d, J = 15.9 Hz, 1H), 7.18
(d, J = 8.0 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H), 7.56 (d,
J = 15.9 Hz, 1H); 13C NMR (50.0 MHz, CDCl3) d
10.4, 13.7, 14.0, 21.5, 22.7, 27.4, 29.0, 29.8, 31.3, 63.0,
124.7, 128.3, 128.5, 129.6, 132.0, 140.7, 142.1, 154.1,
200.5; 119Sn{1H} NMR (101 MHz, CDCl3) d ꢀ41.9;
HRMS (FAB+) Calc. for C25H39O120Sn: M+ – Bu,
475.2023. Found: m/z 475.2013.
mg, 10 lmol) and 1,3-bis(diphenylphosphino)propane
(4.1 mg, 10 lmol) in toluene (0.3 ml) and then a 1,2-
diene (0.60 mmol). The resulting mixture was stirred at
the temperature specified in Table 4, Eqs. (7) and (8).
After the time shown in Table 4, Eqs. (7) and (8), the
reaction mixture was filtered through a Florisil pad.
The filtrate was concentrated and purified by prepara-
tive GPC to give alkynylstannylation products as a mix-
ture of regioisomers. Combined yields are listed in Table
4, Eqs. (7) and (8). Regioisomeric mixtures were sepa-
rated by preparative recycling reversed phase
chromatography.
4.6.3. (E)-4-Butyl-1-(4-chlorophenyl)-5-tributylstannyl-
1,5-hexadien-3-one (12c)
A colorless oil, Rf 0.60 (hexane–ethyl acetate = 10:1).
1H NMR (200 MHz, CDCl3) d 0.72–1.09 (m, 18H),
1.13–1.64 (m, 17H), 1.76–1.96 (m, 1H), 3.49 (t, J = 6.9
Hz, 1H), 5.36 (d, J = 2.1 Hz, 1H), 5.87 (d, J = 2.1 Hz,
1H), 6.76 (d, J = 15.9 Hz, 1H), 7.34 (dt, J = 8.6, 2.1
Hz, 2H), 7.41–7.59 (m, 3H); 13C NMR (50.0 MHz,
CDCl3) d 10.4, 13.7, 14.0, 22.7, 27.4, 29.0, 29.8, 31.0,
63.3, 125.9, 128.9, 129.1, 129.4, 133.3, 136.1, 140.5,
153.8, 200.1; 119Sn{1H} NMR (101 MHz, CDCl3) d
ꢀ41.2; HRMS (FAB+) Calc. for C24H36ClO120Sn: M+
– Bu, 495.1477. Found: m/z 495.1482.
4.7.1.
yne (14a)
A colorless oil, Rf 0.65 (hexane–ethyl acetate = 9:1).
3-Butyl-5-phenyl-2-trimethylstannyl-1-penten-4-
1H NMR (500 MHz, CDCl3) d 0.22 (s, 9H), 0.92 (t,
J = 7.3 Hz, 3H), 1.25–1.70 (m, 6H), 3.41 (t, J = 7.1
Hz, 1H), 5.27 (dd, J = 1.8, 0.9 Hz, 1H), 5.86 (dd,
J = 1.8, 1.2 Hz, 1H), 7.24–7.47 (m, 5H); 13C NMR
(101 MHz, CDCl3) d ꢀ8.4, 14.0, 22.4, 29.5, 35.9,
43.0, 83.7, 92.0, 123.9, 125.3, 127.5, 128.2, 131.5,
155.5; 119Sn{1H} NMR (186 MHz, CDCl3) d ꢀ32.1;
HRMS (ESI) Calc. for C18H26SnNa: M+ + Na,
385.0953. Found: m/z 385.0952. Anal. Calc. for
C18H26Sn: C, 59.87; H, 7.26. Found: C, 59.87; H,
7.23%.
4.6.4. (E)-4-Butyl-1-(4-methoxycarbonylphenyl)-5-trib-
utylstannyl-1,5-hexadien-3-one (12d)
A colorless oil, Rf 0.29 (hexane–ethyl acetate = 10:1).
1H NMR (200 MHz, CDCl3) d 0.73–1.09 (m, 18H),
1.13–1.63 (m, 17H), 1.76–1.97 (m, 1H), 3.51 (t, J = 6.9
Hz, 1H), 3.93 (s, 3H), 5.38 (d, J = 2.2 Hz, 1H), 5.88
(dd, J = 2.2, 0.7 Hz, 1H), 6.86 (d, J = 16.0 Hz, 1H),
7.58 (d, J = 16.0 Hz, 1H), 7.59 (d, J = 8.6 Hz, 2H),
8.04 (d, J = 8.6 Hz, 2H); 13C NMR (50.0 MHz, CDCl3)
d 10.4, 13.6, 14.0, 22.7, 27.4, 29.0, 29.8, 31.0, 52.2, 63.3,
127.5, 128.1, 129.0, 130.0, 131.3, 139.0, 140.5, 153.6,
166.4, 200.0; 119Sn{1H} NMR (101 MHz, CDCl3) d
4.7.2. (Z)-1-Phenyl-4-trimethylstannyl-4-nonen-1-yne (15a)
A colorless oil, Rf 0.64 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.26 (s, 9H), 0.92 (t,
J = 7.0 Hz, 3H), 1.24–1.49 (m, 4H), 2.07 (dd, J = 7.4,
7.1 Hz, 2H), 3.29 (d, J = 1.3 Hz, 2H), 6.27 (tt, J = 7.4,
1.3 Hz, 1H), 7.18–7.46 (m, 5H); 13C NMR (101 MHz,
CDCl3) d ꢀ8.2, 14.1, 22.5, 30.4, 32.2, 34.1, 82.9, 88.8,
124.0, 127.5, 128.2, 131.5, 137.5, 142.1; 119Sn{1H}
NMR (186 MHz, CDCl3) d ꢀ45.0; HRMS (ESI) Calc.
for C18H26SnNa: M+ + Na, 385.0953. Found: m/z
385.0957. Anal. Calc. for C18H26Sn: C, 59.87; H, 7.26.
Found: C, 59.58; H, 7.12%.
ꢀ40.9; HRMS (FAB+) Calc. for C26H39O120Sn: M+
Bu, 519.1921. Found: m/z 519.1925.
–
4.6.5. (E)-3-Butyl-2-tributylstannyl-1,5-octadien-4-one
(12e)
A colorless oil, Rf 0.59 (hexane–ethyl acetate = 10:1).
1H NMR (200 MHz, CDCl3) d 0.69–1.92 (m, 39H),
2.12–2.33 (m, 2H), 3.42 (t, J = 6.9 Hz, 1H), 5.29 (d,
J = 2.2 Hz, 1H), 5.77 (d, J = 2.2 Hz, 1H), 6.12 (dt,
J = 15.7, 1.6 Hz, 1H), 6.89 (dt, J = 15.7, 1.6 Hz, 1H);
13C NMR (50.0 MHz, CDCl3) d 10.4, 12.4, 13.7, 14.0,
22.6, 25.5, 27.4, 29.0, 29.8, 31.3, 62.1, 128.2, 128.6,
148.3, 154.2, 200.8; 119Sn{1H} NMR (101 MHz, CDCl3)
d ꢀ42.3; HRMS (FAB+) Calc. for C20H37O120Sn: M+ –
Bu, 413.1866. Found: m/z 413.1864.
4.7.3. 3-tert-Butyl-5-phenyl-2-trimethylstannyl-1-penten-
4-yne (14c)
A colorless oil, Rf 0.39 (hexane). 1H NMR (500 MHz,
CDCl3) d 0.22 (s, 9H), 1.04 (s, 9H), 3.25 (s, 1H), 5.41 (d,
J = 1.7 Hz, 1H), 5.82 (dd, J = 1.7, 0.9 Hz, 1H), 7.25–7.32
(m, 3H), 7.39–7.43 (m, 2H); 13C NMR (126 MHz,
CDCl3) d ꢀ7.1, 28.2, 34.9, 54.8, 84.5, 92.0, 124.1,
127.5, 128.2, 129.5, 131.5, 153.7; 119Sn{1H} NMR (186
4.7. A general procedure for alkynylstannylation of 1,2-dienes
MHz, CDCl3)
d
ꢀ31.2; HRMS (EI) Calc. for
C17H23Sn: M+ – Me, 347.0821. Found: m/z 347.0826.
Anal. Calc. for C18H26Sn: C, 59.87; H, 7.26. Found:
C, 60.04; H, 7.10%.
To a solution of an alkynylstannane (0.20 mmol)
were added successively a solution of Ni(cod)2 (2.8

Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
3715
4.7.4. (Z)-6,6-Dimethyl-1-phenyl-4-trimethylstannyl-4-
hepten-1-yne (15c)
MHz, CDCl3)
d
ꢀ50.4; HRMS (EI) Calc. for
C23H35Sn: M+ – Bu, 431.1759. Found: m/z 431.1776.
Anal. Calc. for C27H44Sn: C, 66.54; H, 9.10. Found:
C, 66.70; H, 9.01%.
A colorless oil, Rf 0.34 (hexane). 1H NMR (500 MHz,
CDCl3) d 0.30 (s, 9H), 1.09 (s, 9H), 3.29 (d, J = 1.4 Hz,
2H), 6.42 (t, J = 1.4 Hz, 1H), 7.25–7.31 (m, 3H), 7.37–
7.42 (m, 2H); 13C NMR (126 MHz, CDCl3) d ꢀ5.7,
30.9, 33.4, 34.1, 83.4, 89.3, 124.0, 127.5, 128.2, 131.4,
132.2, 154.1; 119Sn{1H} NMR (186 MHz, CDCl3) d
ꢀ43.4; HRMS (EI) Calc. for C17H23Sn: M+ – Me,
347.0821. Found: m/z 347.0818. Anal. Calc. for
C18H26Sn: C, 59.87; H, 7.26. Found: C, 59.60; H,
7.30%.
4.7.9. 3-Butyl-5-(4-trifluoromethylphenyl)-2-trimethyl-
stannyl-1-penten-4-yne (14f)
A colorless oil, Rf 0.43 (hexane). 1H NMR (500 MHz,
CDCl3) d 0.23 (s, 9H), 0.93 (t, J = 7.1 Hz, 3H), 1.30–1.71
(m, 6H), 3.44 (t, J = 7.3 Hz, 1H), 5.30 (dd, J = 2.3, 1.2
Hz, 1H), 5.87 (dd, J = 2.3, 1.2 Hz, 1H), 7.50 (d,
J = 8.2 Hz, 2H), 7.55 (d, J = 8.2 Hz, 2H); 13C NMR
(126 MHz, CDCl3) d ꢀ8.4, 14.0, 22.4, 29.5, 35.7, 43.0,
82.6, 94.9, 124.3 (q, J = 272.1 Hz), 125.1 (q, J = 3.7
Hz), 125.7, 127.7, 129.4 (q, J = 32.5 Hz), 131.7, 154.9;
119Sn{1H} NMR (186 MHz, CDCl3) d ꢀ31.5; HRMS
(EI) Calc. for C18H22F3Sn: M+ – Me, 415.0694. Found:
m/z 415.0689. Anal. Calc. for C19H25F3Sn: C, 53.18; H,
5.87. Found: C, 52.88; H, 5.84%.
4.7.5. 3-Methoxy-5-phenyl-2-trimethylstannyl-1-penten-
4-yne (14d)
A colorless oil, Rf 0.56 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.22 (s, 9H), 3.43 (s,
3H), 4.78 (t, J = 1.4 Hz, 1H), 5.44 (t, J = 1.7 Hz, 1H),
6.07 (t, J = 1.8 Hz, 1H), 7.28–7.34 (m, 3H), 7.42–7.49
(m, 2H); 13C NMR (126 MHz, CDCl3) d ꢀ8.7, 55.9,
77.9, 86.9, 87.8, 122.7, 126.2, 128.2, 128.3, 131.7,
153.6; 119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ30.7;
HRMS (EI) Calc. for C14H17OSn: M+ – Me, 321.0301.
Found: m/z 321.0304.
4.7.10.
(Z)-1-(4-Trifluoromethylphenyl)-4-trimethyl-
stannyl-4-nonen-1-yne (15f)
A colorless oil, Rf 0.39 (hexane). 1H NMR (500 MHz,
CDCl3) d 0.24 (s, 9H), 0.91 (t, J = 7.1 Hz, 3H), 1.28–1.41
(m, 4H), 2.06 (q, J = 7.3 Hz, 2H), 3.29 (s, 2H), 6.25 (t,
J = 7.3 Hz, 1H), 7.48 (d, J = 8.7 Hz, 2H), 7.54 (d,
J = 8.7 Hz, 2H); 13C NMR (126 MHz, CDCl3) d ꢀ8.2,
14.0, 22.4, 30.4, 32.2, 34.1, 81.7, 91.8, 122.9, 125.1 (q,
J = 3.8 Hz), 127.8, 129.3 (q, J = 32.6 Hz), 131.7, 136.9,
142.6; 119Sn{1H} NMR (186 MHz, CDCl3) d ꢀ44.6;
4.7.6. (Z)-1-Methoxy-5-phenyl-2-trimethylstannyl-1-
penten-4-yne (15d)
A colorless oil, Rf 0.50 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.21 (s, 9H), 3.19 (d,
J = 1.4 Hz, 2H), 3.55 (s, 3H), 6.62 (t, J = 1.4 Hz, 1H),
7.23–7.42 (m, 5H); 13C NMR (126 MHz, CDCl3) d
ꢀ9.0, 23.0, 59.0, 81.7, 89.2, 111.9, 123.9, 127.6, 128.2,
131.5, 154.0; 119Sn{1H} NMR (149 MHz, CDCl3) d
ꢀ35.1; HRMS (EI) Calc. for C14H17OSn: M+ – Me,
321.0301. Found: m/z 321.0303.
HRMS (EI) Calc. for C18H22F3Sn: M+
– Me,
415.0694. Found: m/z 415.0693.
4.7.11. 3-Butyl-5-(4-methoxyphenyl)-2-trimethylstannyl-
1-penten-4-yne (14g)
A colorless oil, Rf 0.49 (hexane–ethyl acetate = 9:1).
1H NMR (500 MHz, CDCl3) d 0.21 (s, 9H), 0.92 (t,
J = 7.3 Hz, 3H), 1.30–1.67 (m, 6H), 3.39 (t, J = 7.4
Hz, 1H), 3.80 (s, 3H), 5.26 (dd, J = 1.8, 0.9 Hz, 1H),
5.85 (dd, J = 1.8, 1.2 Hz, 1H), 6.82 (d, J = 9.3 Hz,
2H), 7.34 (d, J = 9.3 Hz, 2H); 13C NMR (126 MHz,
CDCl3) d ꢀ8.4, 14.1, 22.4, 29.5, 36.0, 43.0, 55.2, 83.5,
90.5, 113.8, 116.1, 125.1, 132.8, 155.8, 159.0;
119Sn{1H} NMR (186 MHz, CDCl3) d ꢀ32.7; HRMS
(EI) Calc. for C18H25OSn: M+ – Me, 377.0926. Found:
m/z 377.0910. Anal. Calc. for C19H28OSn: C, 58.34; H,
7.22. Found: C, 58.38; H, 7.31%.
4.7.7. 3-Butyl-5-phenyl-2-tributylstannyl-1-penten-4-yne
(14e)
A colorless oil, Rf 0.43 (hexane). 1H NMR (500 MHz,
CDCl3) d 0.76–1.04 (m, 18H), 1.22–1.64 (m, 18H), 3.38
(t, J = 7.4 Hz, 1H), 5.23 (dd, J = 2.3, 1.0 Hz, 1H), 5.91
(dd, J = 2.3, 0.9 Hz, 1H), 7.24–7.30 (m, 3H), 7.37–7.42
(m, 2H); 13C NMR (126 MHz, CDCl3) d 10.3, 11.6,
13.7, 14.1, 27.4, 29.1, 29.6, 35.8, 43.1, 83.7, 92.2, 124.0,
125.5, 127.5, 128.1, 131.5, 155.0; 119Sn{1H} NMR (186
MHz, CDCl3)
C23H35Sn: M+ – Bu, 431.1759. Found: m/z 431.1770.
d
ꢀ43.2; HRMS (EI) Calc. for
4.7.8. (Z)-1-Phenyl-4-tributylstannyl-4-nonen-1-yne (15e)
A colorless oil, Rf 0.39 (hexane). 1H NMR (500 MHz,
CDCl3) d 0.85–1.06 (m, 18H), 1.25–1.59 (m, 16H), 2.03
(q, J = 7.3 Hz, 2H), 3.27 (d, J = 1.4 Hz, 2H), 6.23 (tt,
J = 7.3, 1.4 Hz, 1H), 7.25–7.30 (m, 3H), 7.37–7.41 (m,
2H); 13C NMR (126 MHz, CDCl3) d 10.4, 13.7, 14.1,
22.6, 27.5, 29.2, 30.7, 32.3, 34.5, 82.9, 89.1, 124.1,
127.5, 128.1, 131.5, 137.0, 142.2; 119Sn{1H} NMR (186
4.7.12. (Z)-1-(4-Methoxyphenyl)-4-trimethylstannyl-4-
nonen-1-yne (15g)
A colorless oil, Rf 0.49 (hexane–ethyl acetate = 9:1).
1H NMR (500 MHz, CDCl3) d 0.23 (s, 9H), 0.90 (t,
J = 7.1 Hz, 3H), 1.18–1.44 (m, 4H), 2.05 (td, J = 7.3,
6.9 Hz, 2H), 3.26 (s, 2H), 3.80 (s, 3H), 6.24 (t, J = 7.3
Hz, 1H), 6.81 (d, J = 8.9 Hz, 2H), 7.32 (d, J = 8.9 Hz,
2H); 13C NMR (126 MHz, CDCl3) d ꢀ8.2, 14.0, 22.4,

3716
Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
30.4, 32.3, 34.1, 55.2, 82.7, 87.2, 113.8, 116.2, 132.8,
137.7, 141.9, 159.0; 119Sn{1H} NMR (149 MHz, CDCl3)
d ꢀ45.3; HRMS (EI) Calc. for C18H25OSn: M+ – Me,
377.0926. Found: m/z 377.0928.
(m, 6H), 1.18–1.68 (m, 6H), 2.06 (dd, J = 7.4, 7.1 Hz,
2H), 3.36 (t, J = 6.6 Hz, 1H), 6.20 (t, J = 7.1 Hz, 1H),
7.23–7.44 (m, 5H); 13C NMR (101 MHz, CDCl3) d
ꢀ7.1, 13.8, 13.9, 20.6, 23.2, 36.1, 38.4, 42.5, 83.5, 92.8,
124.1, 127.4, 128.1, 131.5, 141.2, 144.1; 119Sn{1H}
NMR (186 MHz, CDCl3) d ꢀ49.6; HRMS (ESI) Calc.
for C20H30SnNa: M+ + Na, 413.1266. Found: m/z
413.1260.
4.7.13. 3-Butyl-5-trimethylsilyl-2-trimethylstannyl-1-pen-
ten-4-yne (14j)
A colorless oil, Rf 0.41 (hexane). 1H NMR (500 MHz,
CDCl3) d 0.15 (s, 9H), 0.19 (s, 9H), 0.90 (t, J = 7.1 Hz,
3H), 1.25–1.59 (m, 6H), 3.20 (td, J = 7.4, 0.9 Hz, 1H),
5.22 (dd, J = 2.1, 0.9 Hz, 1H), 5.77 (dd, J = 2.1, 0.9
Hz, 1H); 13C NMR (126 MHz, CDCl3) d ꢀ8.2, 0.2,
14.0, 22.3, 29.3, 35.7, 43.3, 87.4, 109.0, 125.3, 155.3;
119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ31.8; HRMS
(EI) Calc. for C14H27SiSn: M+ – Me, 343.0903. Found:
m/z 343.0907. Anal. Calc. for C15H30SiSn: C, 50.44; H,
8.47. Found: C, 50.67; H, 8.70%.
4.8. A general procedure for alkynylstannylation of allene
A solution of an alkynylstannane (0.20 mmol),
Ni(cod)2 (2.8 mg, 10 lmol), and 1,3-bis(diph-
enylphosphino)propane (4.1 mg, 10 lmol) in toluene
(0.3 ml) was stirred under an atmospheric pressure of al-
lene at the temperature specified in Table 4. After the
time shown in Table 4, the reaction mixture was filtered
through a Florisil pad. The filtrate was concentrated and
purified by preparative GPC to give an alkynylstannyla-
tion product. Yields are listed in Table 4.
4.7.14. (Z)-1-Trimethylsilyl-4-trimethylstannyl-4-nonen-
1-yne (15j)
A colorless oil, Rf 0.40 (hexane). 1H NMR (500 MHz,
CDCl3) d 0.15 (s, 9H), 0.21 (s, 9H), 0.90 (t, J = 7.1 Hz,
3H), 1.28–1.39 (m, 4H), 2.03 (dt, J = 7.3, 6.9 Hz, 2H),
3.09 (d, J = 1.3 Hz, 2H), 6.16 (tt, J = 7.3, 1.3 Hz, 1H);
13C NMR (126 MHz, CDCl3) d ꢀ8.1, 0.1, 14.0, 22.4,
30.9, 32.2, 34.0, 86.9, 105.9, 137.3, 142.1; 119Sn{1H}
NMR (149 MHz, CDCl3) d ꢀ44.9; HRMS (EI) Calc.
for C14H27SiSn: M+ – Me, 343.0903. Found: m/z
343.0892. Anal. Calc. for C15H30SiSn: C, 50.44; H,
8.47. Found: C, 50.05; H, 8.39%.
4.8.1. 5-Phenyl-2-trimethylstannyl-1-penten-4-yne (14b)
A colorless oil, Rf 0.63 (hexane). 1H NMR (300
MHz, CDCl3) d 0.22 (s, 9H), 3.38 (t, J = 1.6 Hz,
2H), 5.30 (dd, J = 3.6, 1.9 Hz, 1H), 5.94 (dd,
J = 3.6, 1.8 Hz, 1H), 7.20–7.47 (m, 5H); 13C NMR
(101 MHz, CDCl3) d ꢀ9.4, 30.3, 83.2, 87.8, 123.8,
125.8, 127.7, 128.2, 131.5, 149.5; 119Sn{1H} NMR
(186 MHz, CDCl3) d ꢀ29.1; HRMS (ESI) Calc. for
C14H18SnNa: M+ + Na, 329.0327. Found: m/z
329.0192. Anal. Calc. for C14H18Sn: C, 55.13; H,
5.95. Found: C, 55.31; H, 5.90%.
4.7.15. 3,3-Dimethyl-5-phenyl-2-trimethylstannyl-1-pen-
ten-4-yne (14k)
A colorless oil, Rf 0.63 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.23 (s, 9H), 1.43 (s,
6H), 5.25 (d, J = 1.4 Hz, 1H), 5.99 (d, J = 1.4 Hz, 1H),
7.18–7.43 (m, 5H); 13C NMR (101 MHz, CDCl3) d
ꢀ7.4, 30.3, 39.6, 82.2, 96.6, 122.0, 123.9, 127.5, 128.1,
131.5, 161.3; 119Sn{1H} NMR (186 MHz, CDCl3) d
ꢀ31.7; HRMS (ESI) Calc. for C16H22SnNa: M+ + Na,
357.0640. Found: m/z 357.0641.
4.8.2. 5-Trimethylsilyl-2-trimethylstannyl-1-penten-4-yne
(14h)
A colorless oil, Rf 0.48 (hexane). 1H NMR (300 MHz,
CDCl3) d 0.16 (s, 9H), 0.19 (s, 9H), 3.19 (t, J = 1.6 Hz,
2H), 5.25 (q, J = 1.9 Hz, 1H), 5.85 (q, J = 1.9 Hz, 1H);
13C NMR (101 MHz, CDCl3) d ꢀ9.2, 0.1, 30.8, 87.2,
104.7, 125.8, 149.2; 119Sn{1H} NMR (149 MHz, CDCl3)
d ꢀ28.3; HRMS (ESI) Calc. for C11H22SiSnNa:
M+ + Na, 325.0409. Found: m/z 325.0582. Anal. Calc.
for C11H22SiSn: C, 43.88; H, 7.36. Found: C, 43.90; H,
7.47%.
4.7.16. 5-Methyl-1-phenyl-4-trimethylstannyl-4-hexen-1-
yne (15k)
A colorless oil, Rf 0.25 (hexane). 1H NMR (500 MHz,
CDCl3) d 0.24 (s, 9H), 1.83 (s, 6H), 3.30 (s, 2H), 7.24–
7.29 (m, 3H), 7.35–7.38 (m, 2H); 13C NMR (126 MHz,
CDCl3) d ꢀ7.8, 19.6, 24.7, 27.8, 81.0, 89.3, 106.7,
124.1, 127.4, 128.1, 131.5, 142.3; 119Sn{1H} NMR (149
4.8.3. 5-Triethylsilyl-2-trimethylstannyl-1-penten-4-yne
(14i)
A colorless oil, Rf 0.72 (hexane). 1H NMR (300 MHz,
CDCl3) d 0.18 (s, 9H), 0.59 (q, J = 8.0 Hz, 6H), 0.99 (t,
J = 8.0 Hz, 9H), 3.21 (t, J = 1.7 Hz, 2H), 5.26 (q, J = 1.7
Hz, 1H), 5.91 (q, J = 1.7 Hz, 1H); 13C NMR (101 MHz,
CDCl3) d ꢀ9.5, 4.4, 7.3, 30.6, 84.6, 105.4, 125.8, 149.2;
119Sn{1H} NMR (149 MHz, CDCl3) d ꢀ28.5; HRMS
(EI) Calc. for C14H28SiSnNa: M+–Me, 329.0746.
Found: m/z 329.0745.
MHz, CDCl3)
C15H19Sn: M+ – Me, 319.0508. Found: m/z 319.0505.
d
ꢀ42.1; HRMS (EI) Calc. for
4.7.17. (Z)-1-Phenyl-3-propyl-4-trimethylstannyl-4-octen-
1-yne (14l)
A colorless oil, Rf 0.67 (hexane–ethyl acetate = 9:1).
1H NMR (300 MHz, CDCl3) d 0.26 (s, 9H), 0.78–1.05

Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
3717
4.9. Synthetic applications
(t, J = 1.2 Hz, 3H), 2.48 (q, J = 7.4 Hz, 2H), 6.85 (t,
J = 1.2 Hz, JSn–H = 109.9 Hz, 1H); 13C NMR (75.5
MHz, CDCl3) d 8.2, 10.7, 13.6, 27.3, 29.1, 36.0, 136.2,
171.8, 200.9; 119Sn{1H} NMR (149 MHz, CDCl3) d
ꢀ43.7; HRMS (ESI) Calc. for C18H36O120SnNa:
M+ + Na, 411.1684. Found: m/z 411.1680.
4.9.1. Cross-coupling reaction of 3j with ethyl 4-
iodobenzoate
A solution of 3j (39 mg, 0.10 mmol) and ethyl 4-iod-
obenzoate (28 mg, 0.10 mmol) in NMP (0.5 ml) was de-
gassed by 4 freeze–thaw cycles. To the degassed solution
was added Pd2(dba)3 (2.3 mg, 2.5 lmol). The resulting
mixture was stirred at 30 ꢁC for 15 h before quenching
with a 1 M KF aqueous solution (1.0 ml) and subse-
quent stirring for 1 h. The whole was filtered through
a Celite pad; the filtrate was extracted with ethyl acetate;
the combined organic extracts were dried over anhy-
drous magnesium sulfate. The crude product was puri-
fied by chromatography on silica gel (hexane–ethyl
acetate = 4:1) to give 5-(4-ethoxycarbonylphenyl)-5-hex-
en-3-one (27) (22 mg, 91% yield) as a colorless oil, Rf
4.9.4. Isomerization of 27
The procedure for 4.9.3 was applied to the reaction
of 27 (25 mg, 0.10 mmol) carried out for 3 h. Purifi-
cation by preparative GPC gave (E)-5-(4-ethoxycarbo-
nylphenyl)-4-hexen-3-one (28) (16.3 mg, 65% yield) as
a pale yellow oil, Rf 0.31 (hexane–ethyl acetate = 4:1).
1H NMR (300 MHz, CDCl3) d 1.13 (t, J = 7.1 Hz,
3H), 1.40 (t, J = 7.1 Hz, 3H), 2.54 (d, J = 1.1 Hz,
3H), 2.59 (q, J = 7.1 Hz, 2H), 4.39 (q, J = 7.1 Hz, 2H),
6.52 (d, J = 1.1 Hz, 1H), 7.53 (d, J = 8.4 Hz, 2H),
8.04 (d, J = 8.4 Hz, 2H); 13C NMR (75.5 MHz,
CDCl3) d 8.0, 14.2, 18.2, 38.0, 61.1, 125.3, 126.5,
129.8, 130.8, 147.1, 152.3, 166.3, 202.0; HRMS (ESI)
Calc. for C15H18O3Na: M+ + Na, 269.1153. Found:
m/z 269.1147.
1
0.24 (hexane–ethyl acetate = 4:1). H NMR (300 MHz,
CDCl3) d 0.99 (t, J = 7.4 Hz, 3H), 1.38 (t, J = 7.1 Hz,
3H), 2.45 (q, J = 7.4 Hz, 2H), 3.61 (s, 2H), 4.36 (q,
J = 7.1 Hz, 2H), 5.23 (s, 1H), 5.66 (s, 1H), 7.43 (d,
J = 8.4 Hz, 2H), 7.99 (d, J = 8.4 Hz, 2H); 13C NMR
(75.5 MHz, CDCl3) d 7.6, 14.1, 35.0, 49.4, 60.9, 118.5,
125.8, 129.8, 141.0, 144.3, 166.4, 208.9; HRMS (ESI)
Calc. for C15H18O3Na: M+ + Na, 269.1153. Found: m/
z 269.1144.
4.9.5. Cross-coupling reaction of 29 with ethyl 4-
iodobenzoate
A procedure similar to 4.9.1 using 29 (38 mg, 0.10
mmol) and 5 mol% of Pd2(dba)3 (4.6 mg, 5.0 lmol)
for 69 h was followed by chromatography on silica
gel (hexane–ethyl acetate = 4:1) to give (E)-5-(4-eth-
oxycarbonylphenyl)-4-hexen-3-one (30) (17 mg, 69%
yield) as a pale yellow oil, Rf 0.31 (hexane–ethyl
acetate = 4:1). 1H NMR (300 MHz, CDCl3) d 1.13
(t, J = 7.1 Hz, 3H), 1.40 (t, J = 7.1 Hz, 3H), 2.54 (d,
J = 1.1 Hz, 3H), 2.59 (q, J = 7.1 Hz, 2H), 4.39 (q,
J = 7.1 Hz, 2H), 6.52 (d, J = 1.1 Hz, 1H), 7.53
(d, J = 8.4 Hz, 2H), 8.04 (d, J = 8.4 Hz, 2H); 13C
NMR (75.5 MHz, CDCl3) d 8.0, 14.2, 18.2, 38.0,
61.1, 125.3, 126.5, 129.8, 130.8, 147.1, 152.3, 166.3,
202.0; HRMS (ESI) Calc. for C15H18O3Na:
M+ + Na, 269.1153. Found: m/z 269.1147.
4.9.2. Cross-coupling reaction of 3o with ethyl 4-
iodobenzoate
The procedure for 4.9.1 was applied to the reaction of
3o (42 mg, 0.10 mmol), the time being 10 h. Purification
by chromatography on silica gel (hexane–ethyl ace-
tate = 4:1) afforded 4,4-dimethyl-5-(4-ethoxycarbonyl-
phenyl)-5-hexen-3-one (32) (20 mg, 73% yield) as a
colorless oil, Rf 0.24 (hexane–ethyl acetate = 4:1). 1H
NMR (300 MHz, CDCl3) d 1.01 (t, J = 7.4 Hz, 3H),
1.30 (s, 6H), 1.38 (t, J = 7.1 Hz, 3H), 2.54 (q, J = 7.4
Hz, 2H), 4.36 (q, J = 7.1 Hz, 2H), 5.35 (s, 1H), 5.41 (s,
1H), 7.16 (d, J = 8.5 Hz, 2H), 7.95 (d, J = 8.4 Hz, 2H);
13C NMR (75.5 MHz, CDCl3) d 8.4, 14.2, 24.9, 30.2,
53.3, 60.9, 116.8, 127.6, 129.4, 146.0, 152.8, 166.5,
214.2; HRMS (ESI) Calc. for C17H22O3Na: M+ + Na,
297.1465. Found: m/z 297.1466.
4.9.6. Cross-coupling reaction of 3j with benzoyl chloride
In a manner similar to 4.9.1, the reaction of 3j (37 mg,
96 lmol) with benzoyl chloride (15 mg, 0.10 mmol) for 8
h followed by chromatography on silica gel (hexane–
ethyl acetate = 4:1) afforded 2-methylene-1-phenyl-1,4-
hexandione (31) (16 mg, 83% yield) as a colorless oil,
Rf 0.34 (hexane–ethyl acetate = 2:1). 1H NMR (300
MHz, CDCl3) d 1.07 (t, J = 7.4 Hz, 3H), 2.56 (t,
J = 7.4 Hz, 2H), 3.62 (s, 1H), 5.78 (s, 1H), 5.92 (s,
1H), 7.34–7.61 (m, 3H), 7.73–7.89 (m, 2H); 13C NMR
(75.5 MHz, CDCl3) d 7.5, 35.8, 46.0, 128.2, 129.1,
129.8, 132.3, 137.4, 142.1, 208.5; HRMS (ESI) Calc.
for C13H14O2Na: M+ + Na, 225.0891. Found: m/z
225.0881.
4.9.3. Isomerization of 3j
To a solution of 3j (194 mg, 0.50 mmol) in THF (5.0
ml) was added NaH (60% dispersion in mineral oil, 4.0
mg, 0.10 mmol), and the resulting mixture was stirred at
room temperature for 4 h before quenching with water
(5.0 ml) and extraction with ethyl acetate (5.0 ml). The
organic layer was separated and dried over anhydrous
magnesium sulfate and concentrated in vacuo. The res-
idue was purified by preparative GPC to give (Z)-5-trib-
utylstannyl-4-hexen-3-one (29) (171 mg, 88% yield) as a
1
colorless oil, Rf 0.67 (hexane–ethyl acetate = 10:1). H
NMR (300 MHz, CDCl3) d 0.77–1.57 (m, 30H), 2,15

3718
Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
4.9.7. Cross-coupling reaction of 14b with iodobenzene
A mixture of 14b (62 mg, 0.20 mmol), iodobenzene (40
mg, 0.20 mmol), and LiCl (13 mg, 0.30 mmol) in DMSO
(1.0 ml) was degassed by four freeze–thaw cycles. To this
were added Pd(PPh3)4 (12 mg, 10 lmol) and CuCl (20 mg,
0.20 mmol), successively. The mixture was stirred for 4.5 h
at 50 ꢁC and then diluted with diethyl ether. The resulting
mixture was treated with a 1 M KF aqueous solution (2.0
ml) for 1 h, and all the insoluble materials were filtered
through a Celite pad. The organic layer was washed with
water (2.0 ml) and then with brine (2.0 ml), dried over
anhydrous magnesium sulfate, and concentrated in va-
cuo. Preparative GPC of the residue gave 2,5-diphenyl-
1-penten-4-yne (33) (38 mg, 87% yield) as an orange solid,
mp 41.5–42.4 ꢁC, Rf 0.53 (hexane–ethyl acetate = 9:1). 1H
NMR (500 MHz, CDCl3) d 3.63 (s, 2H), 5.57 (d, J = 1.4
Hz, 1H), 5.59 (d, J = 0.9 Hz, 1H), 7.28–7.53 (m, 10H);
13C NMR (126 MHz, CDCl3) d 25.8, 83.7, 86.9, 113.8,
123.6, 125.8, 127.77, 127.79, 128.2, 128.3, 131.6, 139.9,
142.5; HRMS (EI) Calc. for C17H14: M+, 218.1095.
Found: m/z 218.1094.
were added Pd(PPh3)4 (12 mg, 10 lmol), CuCl (20 mg,
0.20 mmol), and CuCl2 (27 mg, 0.20 mmol) successively.
The mixture was stirred for 3 h at 50 ꢁC and then diluted
with diethyl ether (5.0 ml). The resulting mixture was
treated with a 1 M KF aqueous solution (1.0 ml) for 3
h and filtered through a Celite pad. The organic layer
was washed with water (1.0 ml) and brine (1.0 ml) and
then dried over anhydrous magnesium sulfate. Evapora-
tion of the solvent followed by preparative GPC gave a
mixture of dl and meso isomers of 4,7-dibutyl-4,5-
dimethylene-1,8-diphenyl-1,7-octadiyne (36a) (32 mg,
82% yield). These diastereomers (36a0 and 36a00) were
separated by preparative recycling reversed phase chro-
matography, although their stereochemistry have not
been determined. 36a0: a colorless oil, Rf 0.14 (hexane).
1H NMR (200 MHz, CDCl3) d 0.89 (t, J = 7.1 Hz,
6H), 1.16–1.89 (m, 12H), 3.65 (dd, J = 8.4, 5.0 Hz,
2H), 5.28 (s, 2H), 5.44 (s, 2H), 7.21–7.51 (m, 10H);
13C NMR (67.8 MHz, CDCl3) d 14.2, 22.6, 29.8, 34.6,
36.9, 83.3, 91.6, 113.9, 123.8, 127.5, 128.1, 131.5,
147.1; HRMS (FAB) Calc. for C30H35: M+ + H,
395.2737. Found: m/z 395.2722. 36a00: a colorless oil,
1
4.9.8. Cross-coupling reaction of 14b with vinyl bromide
The procedure for 4.9.7 was applied to 14b (154 mg,
0.50 mmol) and a 1 M solution of vinyl bromide in THF
(1.5 ml, 1.5 mmol) using Pd2(dba)3 (11.9 mg, 13 lmol) as
a catalyst. Purification by preparative GPC gave 3-
methylene-6-phenyl-1-hexen-5-yne (34) (39 mg, 47%
yield) as a colorless oil, Rf 0.61 (hexane–ethyl ace-
tate = 9:1). 1H NMR (500 MHz, CDCl3) d 3.35 (t,
J = 1.4 Hz, 2H), 5.14 (dd, J = 11.0, 0.9 Hz, 1H), 5.21
(s, 1H), 5.30 (d, J = 17.4 Hz, 1H), 5.50 (t, J = 1.4 Hz,
1H), 6.49 (dd, J = 17.4, 11.0 Hz, 1H), 7.27–7.32 (m,
3H), 7.40–7.46 (m, 2H); 13C NMR (126 MHz, CDCl3)
d 22.4, 83.4, 86.6, 113.8, 117.5, 123.7, 127.8, 128.2,
131.5, 137.7, 140.8; HRMS (EI) Calc. for C13H12: M+,
168.0938. Found: m/z 168.0947.
Rf 0.13 (hexane). H NMR (200 MHz, CDCl3) d 0.91
(t, J = 7.1 Hz, 6H), 1.10–1.86 (m, 12H), 3.52–3.63 (m,
2H), 5.28 (s, 2H), 5.55 (s, 2H), 7.14–7.54 (m, 10H);
13C NMR (50.0 MHz, CDCl3) d 14.1, 22.5, 29.4, 34.4,
36.1, 84.1, 91.1, 113.7, 123.8, 127.7, 128.2, 131.6,
147.2; HRMS (FAB) Calc. for C30H35: M+ + H,
395.2737. Found: m/z 395.2737.
4.9.11. Homo-coupling reaction of 14b
The procedure for 4.9.10 was applied to 14b (154 mg,
0.50 mmol). Purification of the crude product by flash
column chromatography on silica gel (hexane) gave
4,5-dimethylene-1,8-diphenyl-1,7-octadiyne (36b) (61
mg, 73% yield) as a pale yellow solid, mp 101.2–102.3
ꢁC, Rf 0.43 (hexane–ethyl acetate = 9:1). 1H NMR
(500 MHz, CDCl3) d 3.47 (s, 4H), 5.40 (s, 2H), 5.59 (s,
2H), 7.27–7.37 (m, 6H), 7.43–7.51 (m, 4H); 13C NMR
(126 MHz, CDCl3) d 24.8, 83.6, 86.9, 114.0, 123.6,
127.8, 128.2, 131.6, 140.7; HRMS (EI) Calc. for
C22H18: M+, 282.1408. Found: m/z 282.1371.
4.9.9. Cross-coupling reaction of 14b with 1-bromo-2-
phenylethyne
A procedure similar to 4.9.7 using 14b (48 mg, 0.16
mmol) and 1-bromo-2-phenylethyne (37 mg, 0.20 mmol)
followed by preparative GPC gave 3-methylene-1,6-
diphenyl-1,5-hexadiyne (35) (32 mg, 83% yield) as a yel-
1
low oil, Rf 0.54 (hexane–ethyl acetate = 9:1). H NMR
4.9.12. Homo-coupling reaction of 14i
(500 MHz, CDCl3) d 3.43 (t, J = 1.4 Hz, 2H), 5.64 (d,
J = 0.9 Hz, 1H), 5.79 (d, J = 1.4 Hz, 1H), 7.29–7.36
(m, 6H), 7.44–7.50 (m, 4H); 13C NMR (126 MHz,
CDCl3) d 27.5, 84.3, 85.3, 88.8, 90.0, 122.1, 122.9,
123.4, 126.3, 127.9, 128.2, 128.3, 128.4, 131.6; HRMS
(EI) Calc. for C19H14: M+, 242.1095. Found: m/z
242.1078.
In a manner similar to 4.9.10, 14h (4.0 g, 11.7 mmol)
was homo-coupled at 40 ꢁC for 0.8 h. Purification by
flash column chromatography on silica gel (hexane)
gave 4,5-dimethylene-1,8-bis(triethysilyl)-1,7-octadiyne
(36c) (1.53 g, 73% yield) as a pale yellow oil, Rf 0.31
(hexane). 1H NMR (300 MHz, CDCl3) d 0.60 (q,
J = 8.0 Hz, 12H), 0.99 (t, J = 8.0 Hz, 18H), 3.25 (s,
4H), 5.24 (s, 2H), 5.50 (s, 2H); 13C NMR (126 MHz,
CDCl3) d 4.4, 7.3, 25.2, 85.3, 104.7, 113.6, 140.7; HRMS
(ESI) Calc. for C22H38Si2Na: M+ + Na, 381.2408.
Found: m/z 381.2400.
4.9.10. Homo-coupling reaction of 14a
A solution of 14a (73 mg, 0.20 mmol) in DMSO (1.0
ml) was degassed by four freeze–thaw cycles. To this

Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
3719
4.9.13. Desilylation of 36c
yellow oil, Rf 0.42 (hexane–ethyl acetate = 2:1). 1H
NMR (500 MHz, CDCl3) d 1.31 (t, J = 7.1 Hz, 6H),
3.25 (s, 4H), 3.31 (s, 4H), 4.25 (q, J = 7.1 Hz, 4H),
7.24–7.31 (m, 6H), 7.36–7.42 (m, 4H); 13C NMR (126
MHz, CDCl3) d 14.0, 22.6, 32.5, 61.2, 81.5, 86.1,
123.4, 123.9, 127.8, 128.2, 131.6, 132.1, 167.6; HRMS
(ESI) Calc. for C30H28O4Na: M+ + Na, 475.1884.
Found: m/z 475.1885.
To a THF (43 ml) solution of 36c (500 mg, 1.39
mmol) was added AcOH (0.44 g, 7.3 mmol) and TBAF
(5.5 ml, 5.5 mmol, 1 M THF solution) successively at 0
ꢁC. The solution was warmed up to room temperature
and stirred for 45 h. The resulting solution was treated
with water (5.0 ml); the aqueous phase was extracted
for three times with pentane (40 ml). The combined or-
ganic layers were washed for five times with water (5.0
ml) and successively with a saturated NaHCO3 aqueous
solution (5.0 ml) and brine (5.0 ml), and then was dried
over anhydrous sodium sulfate. Careful evaporation of
the solvent followed by purification by flash column
chromatography on silica gel (pentane) gave 4,5-dimeth-
ylene-1,7-octadiyne (36d) [25] (166 mg, 92% yield) as a
4.9.16. Diels–Alder reaction of 36d with diethyl
acetylenedicarboxylate
In a way similar to 4.9.14, 36d (100 mg, 0.77 mmol)
was allowed to undergo the Diels–Alder reaction. Puri-
fication of the product by flash column chromatography
on silica gel (hexane–ethyl acetate = 7:1) gave diethyl
4,5-bis(2-propynyl)-1,4-cyclohexadiene-1,2-dicarboxylate
(37c) (0.23 g, 100% yield) as a colorless oil: Rf 0.22 (hex-
1
colorless oil: Rf 0.44 (hexane–ethyl acetate = 100:1). H
NMR (300 MHz, CDCl3) d 2.18 (t, J = 2.7 Hz, 2H),
3.18–3.23 (m, 4H), 5.29 (s, 2H), 5.49 (s, 2H); 13C
NMR (126 MHz, CDCl3) d 23.8, 71.3, 81.3, 114.2,
140.1.
1
ane–ethyl acetate = 10:1). H NMR (300 MHz, CDCl3)
d 1.31 (t, J = 7.2 Hz, 6H), 2.01 (t, J = 2.7 Hz, 2H), 3.03
(d, J = 2.7 Hz, 4H), 3.15 (s, 4H), 4.24 (q, J = 7.2 Hz,
4H); 13C NMR (126 MHz, CDCl3) d 13.9, 21.4, 32.1,
61.2, 69.5, 80.3, 123.6, 132.0, 167.6; HRMS (EI)
Calc. for C18H20O4: M+, 301.1360. Found: m/z
301.1364.
4.9.14. Diels–Alder reaction of 36a with diethyl
acetylenedicarboxylate
A mixture of 36a (32 mg, 82 lmol) and diethyl acety-
lenedicarboxylate (70 mg, 0.41 mmol) in toluene (0.8 ml)
was stirred for 37 h at 100 ꢁC. Evaporation of the solvent
followed by preparative GPC gave diethyl 4,5-bis(1-bu-
tyl-3-phenyl-2-propynyl)-1,4-cyclohexadiene-1,2-dicarb-
oxylate (37a) (41 mg, 89% yield). These diastereomers
(37a0 and 37a00) were separated by preparative recycling
silica gel chromatography, although their stereochemis-
try could not be determined. 37a0: a colorless oil, Rf
0.20 (hexane–ethyl acetate = 10:1). 1H NMR (200
MHz, CDCl3) d 0.93 (t, J = 6.9 Hz, 6H), 1.22–1.88 (m,
18H), 2.96–3.56 (m, 4H), 3.85 (dd, J = 7.7, 7.1 Hz, 2H),
4.26 (q, J = 7.1 Hz, 4H), 7.22–7.45 (m, 10H); 13C NMR
(67.8 MHz, CDCl3) d 14.1, 22.6, 29.1, 29.8, 33.7, 33.8,
61.2, 82.2, 90.5, 123.5, 127.0, 127.6, 128.1, 131.5, 132.1,
167.7; HRMS (ESI) Calc. for C38H44O4Na: M+ + Na,
587.3135. Found: m/z 587.3115. 37a00: a colorless oil, Rf
0.18 (hexane–ethyl acetate = 10:1). 1H NMR (200
MHz, CDCl3) d 0.84–1.04 (m, 6H), 1.23–1.94 (m, 18H),
2.94–3.55 (m, 4H), 3.85 (dd, J = 9.3, 5.1 Hz, 2H), 4.25
(q, J = 7.1 Hz, 4H), 7.22–7.46 (m, 10H); 13C NMR
(67.8 MHz, CDCl3) d 14.11, 14.14, 22.6, 29.6, 30.1,
33.9, 34.2, 61.2, 82.4, 90.4, 123.5, 127.3, 127.6, 128.0,
131.5, 132.1, 167.6; HRMS (ESI) Calc. for C38H44O4Na:
M+ + Na, 587.3135. Found: m/z 587.3120.
4.9.17. Annulation of 37c with acetylene catalyzed by
Ni(acac)2–DIBAL–PPh3 [26]
A solution of Ni(acac)2 (7.7 mg, 30 lmol) and PPh3
(325 mg, 0.12 mmol) in THF (7.5 ml) was degassed by
four freeze–thaw cycles. To this was added a 1 M solu-
tion of DIBAL in toluene (60 ll, 60 lmol) dropwise at
room temperature. The mixture was stirred at room
temperature for 15 min, and then a solution of 37c (30
mg, 0.1 mmol) in THF (1.0 ml) was added to the mixture
at 0 ꢁC. The resulting mixture was warmed up to room
temperature, stirred for 21 h under an acetylene gas
atmosphere (1 atm), then diluted with ethyl acetate,
and finally filtered through a Florisil pad. Evaporation
of the solvent followed by purification by flash column
chromatography on silica gel (hexane–ethyl ace-
tate = 7:1) gave diethyl 1,4,5,10-tetrahydroanthracene-
2,3-dicarboxylate (38) (18.1 mg, 56% yield) as an orange
solid, mp 82.0–83.3 ꢁC: Rf 0.35 (hexane–ethyl ace-
tate = 7:1). 1H NMR (300 MHz, CDCl3) d 1.32 (t,
J = 7.2 Hz, 6H), 3.04 (s, 4H), 3.31 (s, 4H), 4.26 (q,
J = 7.2 Hz, 4H), 7.11–7.19 (m, 4H); 13C NMR (126
MHz, CDCl3) d 13.9, 32.3, 33.8, 61.1, 122.3, 126.1,
128.0, 132.6, 133.9, 168.0; HRMS (EI) Calc. for
C20H22O4: M+, 326.1517. Found: m/z 326.1511.
4.9.15. Diels–Alder reaction of 36b with diethyl
acetylenedicarboxylate
4.9.18. Tetrahydrotetracene synthesis [27]
To a solution of Cp2ZrCl2 (44 mg, 0.15 mmol) in
THF (4.0 ml) was added n-BuLi (0.19 ml, 0.30 mmol,
1.59 M hexane solution) dropwise at ꢀ78 ꢁC, and the
reaction mixture was stirred at ꢀ78 ꢁC for 1 h. To the
resulting solution was added a THF (1.0 ml) solution
The procedure of 4.9.14 was applied to 36b (14 mg, 50
lmol). Preparative GPC of the crude product gave
diethyl 4,5-bis(3-phenyl-2-propynyl)-1,4-cyclohexadi-
ene-1,2-dicarboxylate (37b) (19 mg, 84% yield) as a pale

3720
Y. Nakao et al. / Journal of Organometallic Chemistry 689 (2004) 3701–3721
of 37b (40 mg, 88 lmol). The mixture was warmed up to
room temperature and stirred for 1 h at room tempera-
ture. To this were added successively CuCl (34 mg, 0.34
mmol), N,N0-dimethylpropyleneurea (58 mg, 0.45
mmol) and o-diiodobenzene (88 mg, 0.26 mmol) at room
temperature, and the whole was stirred at 50 ꢁC for 15 h
before quenching with a 1 M HCl aqueous solution (1.0
ml) and subsequent filtration through a Celite pad. The
organic layer was separated; the aqueous phase was ex-
tracted twice with ethyl acetate (10 ml). The combined
organic extracts were washed with a saturated NaHCO3
aqueous solution (2.0 ml), water (2.0 ml) and brine (2.0
ml) and then dried over anhydrous sodium sulfate.
Evaporation of the solvent followed by purification by
flash column chromatography on silica gel (hexane–
ethyl acetate = 5:1) gave 39 (19 mg, 40% yield) as a pale
yellow solid, mp 138.0–139.2 ꢁC: Rf 0.50 (hexane–ethyl
4.9.20. Synthesis of hexahydroanthracene 41
A mixture of 40 (10 mg, 35 lmol) and diethyl acety-
lenedicarboxylate (48 mg, 0.28 mmol) in toluene (0.5 ml)
was stirred for 28 h at 100 ꢁC. Evaporation of the sol-
vent followed by flash column chromatography on silica
gel (hexane–ethyl acetate = 2:1) gave tetraethyl 1,4-
diphenyl-1,4,5,6,9,10-hexahydroanthracene-2,3,7,8-tetra-
carboxylate (41) (15.3 mg, 70% yield) as a pale yellow
solid, m.p. 138.0–139.2 ꢁC: Rf 0.11 (hexane–ethyl ace-
tate = 4:1). 1H NMR (300 MHz, CDCl3) d 1.00 (t,
J = 7.0 Hz, 6H), 1.25 (t, J = 7.2 Hz, 6H), 2.30–2.47
(m, 4H), 2.64–2.90 (m, 4H), 3.94–4.07 (m, 4H), 4.18
(q, J = 7.2 Hz, 4H), 4.25 (s, 2H), 7.25–7.36 (m, 10H);
13C NMR (126 MHz, CDCl3) d 13.6, 13.9, 31.7, 33.3,
48.3, 60.8, 61.0, 121.3, 125.6, 127.3, 128.6, 129.1,
132.4, 135.1, 140.4, 167.4, 167.9; HRMS (ESI) Calc.
for C38H40O8Na: M+ + Na, 647.2618. Found: m/z
647.2605.
1
acetate = 5:1). H NMR (300 MHz, CDCl3) d 1.27 (t,
J = 7.2 Hz 6H), 2.90 (s, 4H), 3.14 (s, 4H), 4.20 (q,
J = 7.2 Hz, 4H), 7.22–7.60 (m, 14H); 13C NMR (126
MHz, CDCl3) d 13.7, 32.0, 33.6, 60.8, 121.9, 124.8,
125.9, 127.0, 128.5, 129.8, 129.9, 131.2, 132.4, 137.1,
139.6, 167.7; HRMS (ESI) Calc. for C36H32O4Na:
M+ + Na, 551.2196. Found: m/z 551.2200.
References
[1] (a) J.F. Normant, A. Alexakis, Synthesis (1981) 841;
(b) P. Knochel, in: B.M. Trost, I. Fleming, M.F. Semmelhack
(Eds.), Comprehensive Organic Synthesis, vol. 4, Pergamon Press,
New York, 1991, p. 865;
(c) I. Marek, J.F. Normant, in: F. Diederich, P.J. Stang (Eds.),
Metal-Catalyzed Cross-Coupling Reactions, Wiley-VCH, Wein-
heim, 1998, p. 271;
4.9.19. Synthesis of tetrakis(exomethylene)cyclohexane
40 [27]
To a solution of Cp2ZrCl2 (41 mg, 0.14 mmol) in
THF (3.0 ml) was added n-BuLi (0.18 ml, 0.28 mmol,
1.55 M hexane solution) dropwise at ꢀ78 ꢁC, and the
reaction mixture was stirred at ꢀ78 ꢁC for 1 h. To the
resulting solution was added a THF (0.5 ml) solution
of 36b (19.8 mg, 70 lmol). The mixture was warmed
up to room temperature and stirred for 1 h at room tem-
perature. To this were added CuCl (30 mg, 0.30 mmol)
and N,N0-dimethylpropyleneurea (54 mg, 0.42 mmol)
at room temperature and stirred for 2 h before quench-
ing with a 1 M HCl aqueous solution (1.0 ml) and filtra-
tion through a Celite pad. The organic layer was
separated; the aqueous phase was extracted twice with
ethyl acetate (10 ml); the combined organic layer was
washed with a saturated NaHCO3 aqueous solution
(2.0 ml), water (2.0 ml) and brine (2.0 ml) and then dried
over anhydrous sodium sulfate. Evaporation of the sol-
vent followed by purification by flash column chroma-
tography on silica gel (hexane–ethyl acetate = 60:1)
gave (1E,2E)-1,2-bis(phenylmethylene)-4,5-dimethylene-
cyclohexane (40) (10.9 mg, 55% yield) as a pale yellow
solid, mp 119.9–121.3 ꢁC: Rf 0.70 (hexane–ethyl ace-
(d) A.G. Fallis, P. Forgione, Tetrahedron 57 (2001) 5899.
[2] H.G. Richey Jr., S.S. Szucs, Tetrahedron Lett. 12 (1971) 3785.
[3] J.F. Normant, J.-C. Quirion, Y. Masuda, A. Alexakis, Tetrahe-
dron Lett. 31 (1990) 2879.
[4] (a) H. Klein, H. Eijsinga, H. Westmijze, P. Vermeer, Tetrahedron
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