Synthesis and cross-coupling reaction of alkenyl[(2-hydroxymethyl)phenyl]dimethylsilanes

Article abstract of DOI:10.1016/j.jorganchem.2006.04.046

Highly stable alkenyl[2-(hydroxymethyl)phenyl]dimethylsilanes are prepared by stereo- and regioselective hydrosilylation of alkynes catalyzed either by a platinum or ruthenium catalyst using protected [2-(hydroxymethyl)phenyl]dimethylsilanes. Cyclic silyl ether, 1,1-dimethyl-2-oxa-1-silaindan, also serves as a starting material for the alkenylsilanes by the ring-opening reaction with alkenyl Grignard reagents. The resulting alkenylsilanes undergo cross-coupling reaction with various aryl and alkenyl iodides under reaction conditions employing K₂CO₃ as a base at 35-50 °C in highly regio- and stereospecific manners. The reaction tolerates a diverse range of functional groups including silyl protections. The silicon residue is readily recovered and reused on a gram-scale synthesis. Intramolecular coordination of a proximal hydroxyl group is considered to efficiently form pentacoordinate silicates having a transferable group possibly at an axial position and, thus, responsible for the cross-coupling reaction under conditions significantly milder than those reported for the silicon-based reactions.

Full text of DOI:10.1016/j.jorganchem.2006.04.046

Journal of Organometallic Chemistry 692 (2007) 585–603
www.elsevier.com/locate/jorganchem
Synthesis and cross-coupling reaction of
alkenyl[(2-hydroxymethyl)phenyl]dimethylsilanes
*
*
Yoshiaki Nakao , Hidekazu Imanaka, Jinshui Chen, Akira Yada, Tamejiro Hiyama
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
Received 14 March 2006; accepted 18 April 2006
Available online 30 August 2006
Abstract
Highly stable alkenyl[2-(hydroxymethyl)phenyl]dimethylsilanes are prepared by stereo- and regioselective hydrosilylation of alkynes
catalyzed either by a platinum or ruthenium catalyst using protected [2-(hydroxymethyl)phenyl]dimethylsilanes. Cyclic silyl ether, 1,1-
dimethyl-2-oxa-1-silaindan, also serves as a starting material for the alkenylsilanes by the ring-opening reaction with alkenyl Grignard
reagents. The resulting alkenylsilanes undergo cross-coupling reaction with various aryl and alkenyl iodides under reaction conditions
employing K2CO3 as a base at 35–50 ꢀC in highly regio- and stereospecific manners. The reaction tolerates a diverse range of functional
groups including silyl protections. The silicon residue is readily recovered and reused on a gram-scale synthesis. Intramolecular coordi-
nation of a proximal hydroxyl group is considered to efficiently form pentacoordinate silicates having a transferable group possibly at an
axial position and, thus, responsible for the cross-coupling reaction under conditions significantly milder than those reported for the
silicon-based reactions.
ꢁ 2006 Elsevier B.V. All rights reserved.
Keywords: Palladium; Cross-coupling; Silicon; Aryl iodide; Alkenyl iodide
1. Introduction
attractive properties of organosilicon compounds. Since
the pioneering work by Hiyama and Hatanaka [4], in situ
formation of pentacoordinate silicates by use of alke-
nyl(halo)silanes or alkenyl(alkoxy)silanes in the presence
of a fluoride activator has been the standard strategy in
the silicon-based cross-coupling protocol [2]. However,
halosilanes and alkoxysilanes suffer from drawbacks like
sensitivity to heat, moisture, base, and/or acid. A recent
breakthrough in this filed has been initiated independently
by Mori/Hiyama [5] and Denmark [6], who have used alke-
nylsilanols as the coupling agents. Silanols are relatively
stable compared with halosilanes and alkoxysilanes and
allow the cross-coupling reaction to proceed even at room
temperature, significantly milder reaction conditions ever
reported. Furthermore, recent developments in highly sta-
ble tetraorganosilicon reagents, so-called ‘‘masked alkenyl-
silanols’’ that have a labile silacyclobutyl [7], 2-pyridyl [8],
2-thienyl [9], electron-poor aryl [10], benzyl [11], or even
phenyl [12] group, have raised the synthetic potential of
alkenylsilanes as the cross-coupling reagents for synthesis
The metal-catalyzed cross-coupling reactions of main-
group alkenylmetals with organic halides provide a regio-
and stereochemically well-defined access to a range of
substituted ethenes including conjugated arylethenes and
dienes that are ubiquitous functionalities in organic materi-
als and natural products [1]. Among many protocols, a sil-
icon-based one is gaining increasing importance and
interest in view of high stability and non-toxicity of silicon
reagents [2]. Another beneficial aspect of the transforma-
tion is well-established metal-catalyzed alkyne-hydrosilyla-
tion chemistry that makes a variety of alkenylsilanes
readily available in regio-, stereo-, and chemoselective
manners [3]. However, the silicon-based protocol has rarely
been the choice for synthetic chemists irrespective of these
*
Corresponding authors.
E-mail addresses: nakao@npc05.kuic.kyoto-u.ac.jp (Y. Nakao), thiya-
ma@npc05.kuic.kyoto-u.ac.jp (T. Hiyama).
0022-328X/$ - see front matter ꢁ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.04.046

586
Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
of organic materials and complex natural products [13].
They form alkenylsilanols in situ upon treatment with
TBAF or KOSiMe3 to undergo cross-coupling reaction
under mild conditions. Thus, the remaining synthetic prob-
lem in the silicon-based protocol is the use of fluoride acti-
vators, which are relatively expensive and incompatible
with several functional groups including common silyl pro-
tectors. Fluoride-free cross-coupling reactions of alkenyl-
silanes are available, but the number is limited. Herein
the activation is achieved with NaOH [14], KOSiMe3
[12,15], or stoichiometric amount of transition-metal pro-
moters [5] particularly for alkenyl(halo)silanes, alkenyl(alk-
oxy)silanes, or alkenylsilanols.
zyl[2-(hydroxymethyl)phenyl]dimethylsilanes could trans-
fer the allyl or benzyl group to carbonyl compounds [18].
We envisioned that upon treatment with a certain base
alkenyl[2-(hydroxymethyl)phenyl]dimethylsilanes
would
form penta-coordinate silicate intermediates having a
rather electron-withdrawing alkenyl group at an axial posi-
tion and, thus, selectively transfer the alkenyl group among
four different organic substituents. The reagent makes a
variety of alkenyl groups transferable to electrophiles, as
the activating group can function irrespective of the trans-
ferred group [19]. This reagent design has been found to
work well as expected. Reported herein are the details [20].
A clue to an ideal activation of alkenylsilane reagents
has recently been recorded by Takeda and coworkers
who employed alkenyl(trimethyl)silanes having a proximal
hydroxyl group cis to the silyl group to effect smooth trans-
metallation from silicon to copper without fluoride activa-
tion (Fig. 1) [16]. The resulting alkenylcopper reagents
undergo cross-coupling reaction with aryl iodides in the
presence of a palladium catalyst. Shindo also demonstrated
a similar effect of a carboxyl group in a fluoride-free cross
coupling reaction of alkenyl(trimethyl)silanes [17]. These
examples clearly show that intramolecular coordination
by a negatively charged oxygen nucleophile accelerates
transmetallation from silicon to a late transition-metal in
highly efficient manners. However, these precedents are
restricted to alkenylsilanes that have a transferable group
always containing the oxygen-based activating functional-
ity. Accordingly, we have embarked on design of stable
tetraorganosilicon reagents that have an activating organo-
functional group and an independent transferable group to
allow delivery of various organic groups. Indeed, a proto-
type of our alkenylsilane design has been suggested by
Hudrlik and coworkers. They showed that allyl- or ben-
2. Results and discussion
2.1. Preparation of alkenyl[2-(hydroxymethyl)phenyl]-
dimethylsilanes
Key synthetic precursors of alkenyl[2-(hydroxymethyl)
phenyl]dimethylsilanes are readily prepared from 2-bro-
mobenzyl alcohol (Scheme 1). Dimethyl[2-(2-tetrahydro-
2H-pyranoxymethyl)phenyl]silane (1) was obtained by
lithiation of THP-protected 2-bromobenzyl alcohol followed
by trapping with chloro(dimethyl)silane. Attempted depro-
tection of 1 to obtain an unprotected hydrosilane failed but
gave cyclic silyl ether 2, which turned out to be another ver-
satile starting silicon reagent for the alkenylsilanes (vide
infra). Treatment of 2 with LiAlH4 followed by in situ acet-
ylation using acetyl chloride afforded acetyl-protected hyd-
rosilane 3, a reagent complementary to THP-protected
hydrosilane 1.
With the key starting silicon reagents in hand, we then
examined hydrosilylation of alkynes using hydrosilane 1
or 3 to prepare alkenyl[2-(hydroxymethyl)phenyl]dimethyl-
R2
Me Me
Me Si
R1
Me Me
Me Si
R1
Pd(II)
Me Me
Me Me
Si
O
R1
O
O
Si
O
O
R3
Pd(II)
O
R4 R5
Hudrlik's work
R2
R2
Shindo's work
Cu(I)
Takeda's work
Our work
Fig. 1. Organic group transfer from silicon to an electrophile assisted by an intramolecular attack of a negatively charged oxygen.
1)
n
-BuLi (1.1 equiv)
THPO
H
TsOH H2O (2 mol%)
MeOH, rt, 29 h
THF, –78 ˚C
THPO
O
Si
Si
2) HSiMe2Cl (1.2 equiv)
Br
Me2
Me2
˚
–78 C to rt, overnight
1: 83%
2: 83%
1) LiAlH4 (10 equiv)
Et2O, 0 ˚C to rt, 1.7 h
AcO
2
H
Si
2) AcCl (10 equiv)
Me2
3: 67%
˚
0 C to rt, overnight
Scheme 1.

Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
587
Table 1
Preparation of alkenyl[2-(hydroxymethyl)phenyl]dimethylsilanes via hydrosilylation of alkynes catalyzed by Pt/t-Bu3P using hydrosilane 1 or 3 followed
by deprotectiona
R1
R2 (1.0 equiv)
Pt(dvds) (0.1 mol%)
t-Bu3P (0.1 mol%)
H
PGO
H
HO
deprotection
Si
R1
Si =
hexane, 0 oC to rt
Si
Me2
Si
Me2
R2
4
PG = THP: 1
Ac: 3
>95% regio- and
stereoselective
Entry
Alkyne
Hydrosilane
Time (h)
Alkenylsilane
Yieldb (%)
1
2
1
3
2
4
81
82
Si
4a
4c
3
4
5
1
1
1
22c
22
3
84
68
71
NC
Si
NC
4b
MeO2C
Cl
Si
MeO2C
Si
Cl
4d
6
7
3
1
3
3
93
72
t-BuMe2SiO
Si
t-BuMe2SiO
4e
O
N
O
N
Si
O
4f
O
AcO
HO
Si
8
9
1
1
3
5
27d
AcO
4g
43
Si
Me Me
HO
Me Me
4h
10
1
24
57
Me
Si
Me
4i
(continued on next page)

588
Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
Table 1 (continued)
Entry
11
Alkyne
Hydrosilane
Time (h)
2
Alkenylsilane
Yieldb (%)
84
1
Si
Ph
Ph
4j
12
1
18e
81
Si
4k
a
The reaction was carried out using an alkyne (1.0 equiv), a hydrosilane (1.0 equiv), Pt(dvds) (0.1 mol%), and P(t-Bu)3 (0.1 mol%) in hexane at 0 ꢀC to
room temperature. Deprotection was carried out using p-toluenesulfonic acid monohydrate (2 mol%) in MeOH at room temperature for 2–12 h (for 1) or
K2CO3 (20 equiv) in MeOH–H2O (1:1) at 50 ꢀC for 24–60 h (for 3).
b
Isolated yields.
c
Hydrosilylation was carried out at room temperature for 19 h then at 50 ꢀC for 3 h.
Deacetylated product was also obtained in 49% yield.
Hydrosilylation was carried out at rt for 4 h then at 50 ꢀC for 14 h.
d
e
silanes (Table 1). At the onset, we envisaged that protected
hydrosilanes 1 and 3 would act in a manner similar to phe-
nyl(dimethyl)silane, a hydrosilane frequently used for
hydrosilylation of alkynes. Indeed, the equimolar reaction
of hydrosilane 1 with 1-octyne in the presence of
0.1 mol% of platinum-1,3-divinyl-1,1,3,3-tetramethyldi-
siloxane [Pt(dvds)] and P(t-Bu)3 in hexane at 0 ꢀC to room
temperature gave (E)-[2-(hydroxymethyl)phenyl]dimethyl-
(1-octenyl)silane (4a) in 81% yield after deprotection under
acidic conditions regio- and stereoselectively (entry 1). The
same hydrosilylation procedure with 3 followed by depro-
tection under basic conditions also afforded 4a in 82% yield
(entry 2). Thus, one can choose either of the hydrosilane
reagent, 1 or 3, depending on the functional group involved
in a target alkenylsilane. Fair stability of the silicon
reagents toward an acid or base is demonstrated by the
facts that 4a can be purified by silica gel column chroma-
tography without any decomposition and that 4a can be
quantitatively recovered after treatment with a stoichiome-
tric amount of an aqueous 1 M HCl or 1 M NaOH solution
in THF at 50 ꢀC for 24 h.
Under the standard conditions, alkenyl[2-(hydroxy-
methyl)phenyl]dimethylsilanes (4b–4f) having a functional
group such as cyano, ester, chloro, silyloxy, or N-phthali-
mide were prepared in good yields (entries 3–7), whereas
an acetoxy-bearing one (4g) was obtained in only 27% yield
due to formation of a significant amount of deacetylated
product during the THP deprotection (entry 8). Hydrosily-
lation of 1-methyl-3-butyn-2-ol gave the corresponding
alkenylsilane (4h) in 43% yield and an allylsilane A (ca.
40% yield), possibly derived from an intramolecular SN20
type attack of the hydroxymethyl group assisted by an acid
catalyst (entry 9 and Scheme 2) [21]. Conjugated butadi-
enylsilane 4i and (E)-styrylsilane 4j were prepared in good
yields from 2-methyl-1-buten-3-yne and phenylacetylene,
respectively (entries 10 and 11). An internal alkyne, 4-
octyne, also underwent the present hydrosilylation stere-
oselectively to give (E)-4-octenylsilane 4k (entry 12).
Ruthenium-catalyzed hydrosilylation has recently
emerged as a unique tool for preparation of (Z)-alkenylsil-
anes via trans-addition of hydrosilanes across alkynes
[10,22]. Employing the protocol reported by Ozawa and
coworkers [10], we prepared (Z)-styrylsilane 4l in 72% yield
by the hydrosilylation of phenylacetylene with 1 in the
presence of a ruthenium catalyst followed by acidic depro-
tection (Eq. (1)).
HO
TsOH•H2O
(2 mol%)
RuHCl(CO)[P(
(5 mol%)
i-Pr) ]
3 2
THPO
H
+
Ph
Si
Si
CH2Cl2, rt, 3 h
MeOH, rt, 9 h
Me2
Me2
1:1
Ph
4l: 72%
1
ð1Þ
Ring-opening reactions of cyclic silyl ether 2 with alke-
nyl Grignard reagents represent another way to prepare
various alkenyl[2-(hydroxymethyl)phenyl]dimethylsilanes
(Eq. (2)). The procedure is straightforward and useful par-
ticularly when the corresponding Grignard reagents and/or
alkenyl halides are readily available from commercial
sources.
HO
R3
R3
R1
O
+
Si
MgBr
Si
Et2O or THF
0 ˚C to rt
Me2
R1
Me2
R2
R2
2
Me
O
HO
Me
Me
H2O
R1 = R2 = R3 = H: 4m (81%)
R
R
1 = R3 = H; R2 = Me: 4n [94%, Z:E = 94:6]
1 = R2 = H; R3 = Me: 4o (89%)
Me
Si
Si
– H2O
– H
Me2
Me2
R1 = R2 = H; R3 = Ph: 4p (56%)
R1 = R2 = Me; R3 = H: 4q (71%)
A: ca. 40%
ð2Þ
Scheme 2.

Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
589
2.2. Cross-coupling reaction of alkneyl[2-
(hydroxymethyl)phenyl]dimethylsilanes with aryl and
alkenyl iodides
(entry 19). Vinylsilane 4m and other mono- and disubsti-
tuted alkenylsilanes 4i–4q also reacted with ethyl 4-
iodobenzoate (5b) in stereo- and regiospecific manners giv-
ing the desired arylethenes in good yields (entries 21–30).
Especially, regiospecific reaction of 4p with both activated
and unactivated aryl iodides is remarkable in view that the
corresponding coupling of fluorosilanes results in cine-sub-
stitution to some extent (entries 28 and 29) [23].
The cross-coupling reactions of 4b with (E)- and (Z)-1-
iodo-1-octene (7a and 7b) also proceeded stereospecifically
to give 1,4-disubstituted 1,3-diene products 8ba and 8bb in
73% and 78% yields, respectively (Eq. (3)). Use of N-(2-
diphenylphosphinobenzylidene)cyclohexylamine (9) as a
ligand rather than tri(2-furyl)phosphine was found effective
for the present diene formation [24].
To prove the viability of our reagent design, we first
examined the reaction of (E)-1-octenylsilane 4a
(0.39 mmol) with 4-cyanoiodobenzene (5a: 0.30 mmol) in
the presence of [(g3-C3H5)PdCl]2 (0.5 mol%), tri-2-furyl-
phosphine (2.0 mol%), and a metal carbonate (0.78 mmol)
at 35 ꢀC (Table 2). Among the bases we examined, use of
inexpensive K2CO3 in a polar DMSO solvent turned out
satisfactory and gave (E)-1-(4-cyanophenyl)-1-octene (6aa)
quantitatively (entry 3), whereas relatively more basic
Cs2CO3 was best in THF (entry 4). Na2CO3 was com-
pletely ineffective for the present coupling reaction even
in DMSO (entry 1). Stronger bases like NaOH and n-
BuLi were also effective in THF (entries 5 and 6), showing
base flexibility to tune a base depending on substrate
structures.
We further found that PdCl2 was equally effective as
[(g3-C3H5)PdCl]2 on a larger scale (entry 1 of Table 3),
and then extended the reaction of alkneyl[2-(hydroxy-
methyl)phenyl]dimethylsilanes (1.1 mmol) to various aryl
iodides (1.0 mmol) under the optimized conditions employ-
ing mild and inexpensive K2CO3 as a base (Table 3). Aryl
iodides having electron-withdrawing or -donating func-
tional groups such as ester, keto, formyl, nitro, chloro,
and methoxy also underwent the reaction in good yields
(entries 2–7). It is worth noting that both silyl-protected
and unprotected hydroxyl groups tolerated the present pro-
tocol (entries 8 and 9). ortho-Substituents did not affect the
reaction (entries 10 and 11); such heteroaryl iodides as 3-
iodopyridine and 2-iodothiophene both reacted in good
yields (entries 12 and 13). Functional groups in alkenyl[2-
(hydroxymethyl)phenyl]dimethylsilanes are also compati-
ble with the present conditions (entries 14–20); arylethene
having an allyl acetate moiety 6gb may find further appli-
cations as a substrate for rich chemistry of p-allylpalladium
PdCl2 (1 mol%)
9 (1 mol%)
K2CO3 (2.2 equiv)
HO
I
+
NC
Hex
Hex
(E): 7a
1.1:1.0
NC
Si
DMSO, 35 ˚C
Me2
(5E,7E): 8ba, 73% (3 h)
(5E,7Z): 8bb, 78% (2 h)
4b
NCy
PPh2
(Z):7b
9
ð3Þ
A gram-scale synthesis was examined using 9.1 g
(33 mmol) of 4a and 8.3 g (30 mmol) of 5b under the iden-
tical conditions. Cyclic silyl ether 2 was recovered by distil-
lation in 62% yield based on the aryl iodide; the residue was
chromatographed to give the desired coupling product 6ab
in 97% yield (Eq. (4)). As demonstrated above (Scheme 1
and Table 1), the silyl residue 2 is the starting reagent for
the synthesis of the alkenylsilanes. Namely, the metal resi-
due of the cross-coupling is demonstrated for the first time
to be reused for the next coupling.
30 mmol
scale
I
Hex
HO
O
+
+
Hex
Si
Si
CO2Et
CO2Et
Me2
Me2
4a
9.1 g
5b
8.3 g
6ab
7.6 g, 97%
2
3.1g, 62%
ð4Þ
Table 2
Cross-coupling reaction of (E)-[2-(hydroxymethyl)phenyl]dimethyl(1-octenyl)silane (4a) with 4-cyanoiodobenzene (5a)a
[(η3-C3H5)PdCl]2 (0.5 mol%)
(2-furyl)3P (2 mol%)
Base (2.6 equiv)
HO
I
Hex
+
Hex
Si
Solvent, 35 ˚C
CN
CN
Me2
4a
1.3:1.0
5a
6aa
Entry
Base
Solvent
Time (h)
Yieldb (%)
1
2
3
4
5
6c
a
Na2CO3
K2CO3
K2CO3
Cs2CO3
10 M NaOH aq.
n-BuLi
DMSO
THF
DMSO
THF
THF
THF
31
48
5
19
5
<5
44
100
88
93
96
1.5
The reaction was carried out using 4a (0.39 mmol), 5a (0.30 mmol), a base (0.78 mmol), [(g3-C3H5)PdCl]2 (1.5 lmol), and (2-furyl)3P (6.0 lmol) in a
solvent (0.75 mL) at 35 ꢀC.
b
Estimated by GC using pentadecane as an internal standard.
4a was treated with n-BuLi (0.39 mmol) in THF at 0 ꢀC to room temperature before addition of 5a, PdCl2, and (2-furyl)3P.
c

590
Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
Table 3
Cross-coupling reaction of alkenyl[2-(hydroxymethyl)phenyl]dimethylsilanes with aryl iodidesa
PdCl2 (1 mol%)
(2-furyl)3P (2 mol%)
HO
R3
R3
K2CO3 (2.2 equiv)
Ar
+
Si
I Ar
R1
Me2
R1
DMSO, 35–50˚C
R2
6
R2
4
1.1:1.0
5
Entry
1
Alkenylsilane
I–Ar
Time (h)
20
Product
Yieldb (%)
93
4a
CN
CN
I
Hex
5a
6aa
2
3
4
5
6
4a
4a
4a
4a
4a
18
17
20
26
19
96
94
94
99
93
CO2Et
CO2Et
I
I
Hex
Hex
5b
6ab
Ac
Ac
5c
6ac
CHO
NO2
Cl
CHO
NO2
Cl
Hex
Hex
I
I
5d
6ad
5e
5f
6ae
6af
I
Hex
7
4a
40
89
OMe
OMe
Hex
I
5g
6ag

Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
591
Table 3 (continued)
Entry
8
Alkenylsilane
I–Ar
Time (h)
23
Product
Yieldb (%)
98
4a
4a
4a
OSiMe2t-Bu
5h
OSiMe2t-Bu
I
Hex
6ah
9
47
47
88
94
OH
OH
I
Hex
Hex
Hex
5i
6ai
10
Me
Me
I
5j
6aj
11
4a
23
91
I
5k
6ak
12
4a
23
80
N
N
I
I
Hex
Hex
5l
6al
13
14
4a
4b
23
19
99
95
S
S
5m
6am
5b
CO2Et
NC
6bb
15
16
4c
5b
18
50
92
CO2Et
MeO2C
6cb
4d
5b
92
CO2Et
Cl
6db
(continued on next page)

592
Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
Table 3 (continued)
Entry
17
Alkenylsilane
I–Ar
Time (h)
31
Product
Yieldb (%)
90
4e
5b
CO2Et
t-BuMe2SiO
6eb
18
4f
5b
24
93
O
CO2Et
N
6fb
O
19c
4g
5b
25
93
CO2Et
AcO
HO
6gb
20d,e
4h
5b
72
92
CO2Et
Me Me
6hb
21
4i
5b
25
93
CO2Et
Me
6ib
22
4j
5b
19
88
CO2Et
Ph
6jb
23d
4k
5b
29
92
CO2Et
6kb
24
4l
5b
11
92
CO2Et
Ph
6lb

Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
593
Table 3 (continued)
Entry
25
Alkenylsilane
I–Ar
Time (h)
19
Product
Yieldb (%)
87
4m
5b
CO2Et
CO2Et
CO2Et
6mb
6nb
26
4n
5b
19
91f
Me
27
4o
5b
24
96
Me 6ob
28
4p
4p
4q
5b
5g
5b
25
12
25
95
CO2Et
OMe
Ph 6pb
29c,d
80g
Ph 6pg
30
96
CO2Et
Me
Me
6qb
a
The reaction was carried out using an alkenylsilane (1.1 mmol), an aryl iodide (1.0 mmol), K2CO3 (2.2 mmol), PdCl2 (10 lmol), and (2-furyl)3P
(20 lmol) in DMSO (2.5 mL) at 35 ꢀC.
b
Isolated yields.
1.3 mmol of the alkenylsilane was used.
The reaction was carried out at 50 ꢀC.
PdCl2 (50 lmol) and (2-furyl)3P (0.10 mmol) were used.
Z:E = 94:6 estimated by GC.
cine-Product was found at best in 4% yield.
c
d
e
f
g
3. Conclusion
certainly allow convenient preparation of a wide range
of functionalized conjugated arylethenes and dienes
through the silicon-based cross-coupling reaction, and,
thus, will find a widespread synthetic applications both
in academia and industry. Current efforts are also direc-
ted to other metal-catalyzed reactions using these
reagents.
A new silicon-based cross-coupling protocol is demon-
strated that employs alkenyl[2-(hydroxymethyl)phenyl]-
dimethylsilanes under mild conditions employing K2CO3
as a base. Highly chemoselective transformations of the
highly stable alkenylsilane reagents presented herein

594
Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
4. Experimental
4.1. General remarks
diethyl ether, and the combined organic layers were washed
with brine and dried over anhydrous MgSO4. Distillation
under vacuum gave 1 (38 g, 83%) as a colorless oil, bp
1
135 ꢀC (1.0 mmHg). H NMR (400 MHz, CDCl3) d 7.54
All manipulations of oxygen- and moisture-sensitive
materials were conducted with a standard Schlenk tech-
nique under an argon atmosphere. Flush column chroma-
tography was performed using Merck silica gel 60
(40–63 lm), Kanto Chemical silica gel (spherical, 40–50
lm), or Merck aluminium oxide 90 neutral (20–63 lm).
Analytical thin layer chromatography (TLC) was per-
formed on Merck Kieselgel 60 F254 (0.25 mm) plates. Visu-
alization was accomplished with UV light (254 nm) and/or
an aqueous alkaline KMnO4 solution followed by heating.
Proton and carbon nuclear magnetic resonance spectra (1H
NMR and 13C NMR) were recorded on a Varian Mercury
400 (1H NMR, 400 MHz; 13C NMR, 101 MHz) spectrom-
eter with solvent resonance as the internal standard (1H
NMR, CHCl3 at 7.26 ppm; 13C NMR, CDCl3 at
77.0 ppm). 1H NMR data are reported as follows: chemical
shift, multiplicity (s = singlet, d = doublet, t = triplet,
q = quartet, quint = quintet, sext = sextet, br = broad,
m = multiplet), coupling constants (Hz), and integration.
GC analyses were performed on a Shimadzu GC 2010
equipped with a DB-5 column (30 m · 0.53 mm, pressur-
e = 31.7 kPa, detector = FID, 290 ꢀC) with helium gas as
a carrier. Melting points were determined using a
YANAKO MP-500D. Mass spectra were obtained with a
JEOL JMS-700 (EI at 70 eV unless otherwise stated or
CI) or JEOL JMS-HX110A (FAB) spectrometer. Unless
otherwise noted, reagents were commercially available
and were used without purification. THF and diethyl ether
were distilled from sodium/benzophenone ketyl right
before use. Anhydrous DMSO was purchased from
Aldrich and used without further purification. N-(2-Diph-
enylphosphinobenzylidene)cyclohexylamine (9) [25] and
RuHCl(CO)[P(i-Pr)3]2 [26] were prepared according to
the reported procedures.
(dd, J = 7.2, 1.4 Hz, 1H), 7.44 (dd, J = 7.5, 0.5 Hz, 1H),
7.37 (td, J = 7.5, 1.5 Hz, 1H), 7.29 (td, J = 7.3, 1.3 Hz,
1H), 4.86 (d, J = 11.9 Hz, 1H), 4.73 (t, J = 3.6 Hz, 1H),
4.59 (d, J = 11.7 Hz, 1H), 4.56–4.51 (m, 1H), 3.98–3.89
(m, 1H), 3.60–3.52 (m, 1H), 1.94–1.45 (m, 6H), 0.364 (d,
J = 3.7 Hz, 3H), 0.360 (d, J = 3.7 Hz, 3H); 13C NMR
(101 MHz, CDCl3) d 143.6, 136.5, 134.7, 129.4, 128.3,
127.0, 98.1, 69.1, 62.1, 30.6, 25.5, 19.3, ꢀ3.0, ꢀ3.1; IR
(neat) 2943, 2124, 1250, 1202, 1119, 1080, 1055, 1026,
974, 885, 837, 752 cmꢀ1; MS (EI) m/z (%) 250 (M+, 0.1),
164 (12), 163 (14), 150 (17), 149 (100), 85 (22). Anal. Calc.
for C14H22O2Si: C, 67.15; H, 8.86. Found: C, 67.44; H,
8.91%.
4.3. Preparation of 1,1-dimethyl-2-oxa-1-silaindan (2)
p-Toluenesulfonic acid monohydrate (1.14 g, 6.0 mmol)
was added portionwise to 1 (75 g, 0.30 mol) dissolved in
MeOH (500 mL) at rt, and the mixture was stirred for
16 h before concentration in vacuo. The residue was dis-
tilled to give 2 (41 g, 83%) as a colorless oil, bp 45 ꢀC
(2.0 mmHg). 1H NMR (400 MHz, CDCl3) d 7.59 (dd,
J = 7.1, 0.4 Hz, 1H), 7.42–7.37 (m, 1H), 7.33–7.28 (m,
1H), 7.23 (dd, J = 7.5, 0.7 Hz, 1H), 5.16 (s, 2H), 0.40 (s,
6H); 13C NMR (101 MHz, CDCl3) d 149.7, 135.0, 131.0,
129.5, 126.8, 121.6, 71.5, 0.6; IR (neat) 3360, 3057, 2953,
2897, 2860, 1701, 1593, 1445, 1350, 1252, 1200, 1134,
1067, 1051, 1024, 858, 829, 791, 748, 692, 652 cmꢀ1; MS
(EI) m/z (%) 165 (M+, 9), 164 (58), 163 (26), 151 (13),
150 (45), 149 (100), 105 (15). Anal. Calc. for C9H12OSi:
C, 65.80; H, 7.36. Found: C, 65.60; H, 7.34%.
4.4. Preparation of dimethyl[2-(2-acetoxymethyl)phenyl]-
silane (3)
4.2. Preparation of dimethyl[2-(2-tetrahydro-2H-
pyranoxymethyl)phenyl]silane (1)
To a suspension of LiAlH4 (0.38 g, 10.0 mmol) in
diethyl ether (30 mL) was added 2 (1.64 g, 10.0 mmol) at
0 ꢀC, and the resulting mixture was stirred at rt for
100 min before addition of acetyl chloride (7.1 mL,
100 mmol) at 0 ꢀC. Stirring was continued at rt overnight,
and the mixture was filtered through a Celite and then
through a silica gel pad. The residue was purified by flash
chromatography on silica gel to give 3 (1.39 g, 67%) as a
colorless oil, Rf 0.30 (hexane–ethyl acetate = 20:1). 1H
NMR (400 MHz, CDCl3) d 7.57 (d, J = 7.0 Hz, 1H),
7.42–7.32 (m, 3H), 5.20 (s, 2H), 4.58–4.51 (m, 1H), 2.10
(s, 3H), 0.37 (d, J = 3.8 Hz, 6H); 13C NMR (101 MHz,
CDCl3) d 170.8, 140.9, 137.2, 135.0, 129.6, 129.1, 127.8,
66.6, 21.1, ꢀ3.1; IR (neat) 2959, 2127, 1742, 1437, 1379,
To
a
mixture of 2-bromophenylmethanol (34 g,
0.180 mol) and 3,4-dihydro-2H-pyran (18.2 g, 0.22 mol)
were added 10 drops of concentrated hydrochloric acid,
and the resulting mixture was stirred at rt overnight. The
mixture was diluted with diethyl ether, neutralized with a
saturated NH4Cl aqueous solution, dried over anhydrous
MgSO4, and concentrated in vacuo to give 2-(2-tetrahy-
dro-2H-pyranoxymethyl)bromobenzene, which was dis-
solved in THF (450 mL). To the solution was added a
1.6 M n-BuLi solution in hexane (124 mL, 0.20 mol) over
40 min at ꢀ78 ꢀC, and the resulting solution was stirred
for 50 min before the addition of chlorodimethylsilane
(20 g, 0.22 mol) at ꢀ78 ꢀC. The mixture was warmed grad-
ually at rt overnight and quenched with H2O. After evap-
oration of the solvents, the residue was extracted with
1362, 1236, 1130, 1080, 1026, 966, 887, 839, 756 cmꢀ1
;
MS (EI) m/z (%) 208 (M+, 6), 207 (37), 194 (14), 193
(81), 165 (59), 163 (24), 152 (25), 151 (98), 150 (29), 149
(100), 148 (24), 147 (27), 145 (12), 135 (27), 134 (12), 133

Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
595
(55), 131 (11), 123 (14), 121 (14), 119 (13), 117 (38), 105
(20), 91 (34), 75 (46). Anal. Calc. for C11H16O2Si: C,
63.42; H, 7.74. Found: C, 63.48; H, 7.74%.
for C15H21NOSi: C, 69.45; H, 8.16. Found: C, 69.68; H,
8.15%.
4.5.3. Methyl (E)-6-([2-(hydroxymethyl)phenyl]-
dimethylsilyl)-5-hexenoate (4c)
4.5. Preparation of (E)-alkenyl[2-(hydroxymethyl)-
phenyl]dimethylsilanes by platinum-catalyzed
hydrosilylation using 1
Following the procedure for 4a, the reaction using hyd-
rosilane 1 (2.5 g, 10.0 mmol) and methyl 5-hexynoate
(1.26 g, 10.0 mmol) gave 4 c (2.0 g, 68%) as a colorless
oil, Rf 0.38 (hexane–ethyl acetate = 3:1). 1H NMR
(400 MHz, CDCl3) d 7.53 (dd, J = 7.4, 1.4 Hz, 1H), 7.47
(d, J = 7.1 Hz, 1H), 7.40 (td, J = 7.4, 1.5 Hz, 1H), 7.28
(td, J = 7.5, 1.3 Hz, 1H), 6.10 (dt, J = 18.7, 6.2 Hz, 1H),
5.87 (dt, J = 18.7, 1.5 Hz, 1H), 4.74 (s, 2H), 3.65 (s, 3H),
2.31 (t, J = 7.5 Hz, 2H), 2.19 (td, J = 7.4, 6.2 Hz, 2H),
1.76 (quint, J = 7.4 Hz, 2H), 1.66 (bs, 1H), 0.39 (s, 6H);
13C NMR (101 MHz, CDCl3) d 174.0, 147.6, 146.5,
136.7, 135.1, 129.8, 129.7, 127.9, 127.0, 65.3, 51.5, 35.9,
33.4, 23.7, ꢀ1.2; IR (neat) 3447, 2951, 1738, 1616, 1437,
1250, 1202, 1078, 991, 839, 750 cmꢀ1. Anal. Calc. for
C16H24O3Si: C, 65.71; H, 8.27. Found: C, 65.66; H, 8.12%.
4.5.1. (E)-[2-(Hydroxymethyl)phenyl]dimethyl(1-
octenyl)silane (4a)
To a solution of hydrosilane 1 (10.0 g, 0.040 mol) and 1-
ocytne (4.4 g, 0.040 mol) in hexane (4 mL) were added a
10% hexane solution of t-Bu3P (80 mg, 0.040 mmol) and a
0.01 M hexane solution of platinum(0)-1,3-divinyl-1,1,3,3-
tetramethyldisiloxane complex (4.0 mL, 0.040 mmol) at
0 ꢀC. The resulting mixture was stirred at rt for 2 h, filtered
through a Florisil pad, and concentrated in vacuo. The res-
idue was dissolved in MeOH (140 mL) and treated with
p-toluenesulfonic acid monohydrate (152 mg, 0.80 mmol)
at rt for 4 h. After removal of the solvent in vacuo, the res-
idue was purified by flash chromatography on silica gel to
give the title compound (9.0 g, 81%) as a colorless oil, Rf
4.5.4. (E)-5-Chloro-1-pentenyl[2-(hydroxymethyl)-
phenyl]dimethylsilane (4 d)
1
0.25 (hexane–ethyl acetate = 10:1). H NMR (400 MHz,
CDCl3) d 7.55 (dd, J = 7.3, 1.3 Hz, 1H), 7.46 (dd, J = 7.5,
0.7 Hz, 1H), 7.40 (td, J = 7.5, 1.5 Hz, 1H), 7.28 (td,
J = 7.3, 1.3 Hz, 1H), 6.15 (dt, J = 18.7, 6.4 Hz, 1H), 5.83
(dt, J = 18.7, 1.5 Hz, 1H), 4.74 (s, 2H), 2.17–2.12 (m, 2H),
1.63 (br s, 1H), 1.42–1.25 (m, 8H), 0.90–0.83 (m, 3H),
0.39 (s, 6H); 13C NMR (101 MHz, CDCl3) d 149.7, 146.4,
137.1, 135.1, 130.0, 128.2, 128.0, 127.0, 65.4, 36.8, 31.7,
28.9, 28.5, 22.6, 14.1, ꢀ1.2; IR (neat) 3329, 2957, 2926,
2855, 1614, 1466, 1435, 1248, 1126, 1078, 991, 841, 783,
746, 687 cmꢀ1; MS (EI) m/z (%) 276 (M+, 0.1), 261 (32),
243 (14), 199 (12), 177 (13), 173 (11), 166 (27), 165 (66),
164 (51), 163 (44), 160 (11), 159 (42), 151 (25), 150 (30),
149 (100), 148 (27), 147 (50), 146 (16), 145 (51), 137 (12),
135 (31), 133 (14), 131 (22), 129 (18), 105 (16), 91 (18), 75
(32), 61 (39), 59 (13), 55 (11). Anal. Calc. for C17H28OSi:
C, 73.85; H, 10.21. Found: C, 73.86; H, 10.42%.
The procedure for 4a was applied to the reaction of hyd-
rosilane 1 (2.5 g, 10.0 mmol) and 5-chloro-1-pentyne (1.03
g, 10.0 mmol) to give the title compound (1.91 g, 71%) as
1
a colorless oil, Rf 0.15 (hexane–ethyl acetate = 10:1). H
NMR (400 MHz, CDCl3) d 7.54 (dd, J = 7.3, 1.3 Hz,
1H), 7.47 (dd, J = 7.5, 0.6 Hz, 1H), 7.40 (td, J = 7.5,
1.3 Hz, 1H), 7.29 (td, J = 7.3, 1.5 Hz, 1H), 6.10 (dt, J =
18.7, 6.2 Hz, 1H), 5.92 (dt, J = 18.5, 1.5 Hz, 1H), 4.74 (s,
2H), 3.53 (t, J = 6.6 Hz, 2H), 2.31 (tdd, J = 6.6, 6.2,
1.5 Hz, 2H), 1.89 (quint, J = 6.6 Hz, 2H), 1.59 (bs, 1H),
0.40 (s, 6H); 13C NMR (101 MHz, CDCl3) d 146.9,
146.4, 136.7, 135.1, 130.2, 129.7, 128.0, 127.0, 65.4, 44.4,
33.7, 31.3, ꢀ1.2; IR (neat) 3369, 2955, 1614, 1435, 1250,
1124, 1078, 991, 839, 750, 650 cmꢀ1. Anal. Calc. for C14H21-
ClOSi: C, 62.54; H, 7.87. Found: C, 62.31; H, 7.70%.
4.5.5. (E)-N-[3-([2-(Hydroxymethyl)phenyl]-
dimethylsilyl)-2-propenyl]phthalimide (4f)
4.5.2. (E)-5-Cyano-1-pentenyl[2-(hydroxymethyl)-
phenyl]dimethylsilane (4b)
Following the procedure for 4a, the reaction using hyd-
rosilane 1 (2.5 g, 10.0 mmol) and N-propargylphthalimide
(1.85 g, 10.0 mmol) gave 4f (2.5 g, 72%) as a colorless solid
(mp = 88.6–89.2 ꢀC), Rf 0.10 (hexane–ethyl acetate = 5:1).
1H NMR (400 MHz, CDCl3) d 7.88–7.82 (m, 2H), 7.75–
7.69 (m, 2H), 7.49 (dd, J = 7.3, 1.3 Hz, 1H), 7.46 (d,
J = 7.0 Hz, 1H), 7.38 (td, J = 7.3, 1.3 Hz, 1H), 7.26 (td,
J = 7.3, 1.3 Hz, 1H), 6.12 (dt, J = 18.6, 4.5 Hz, 1H), 6.00
(dt, J = 18.6, 1.4 Hz, 1H), 4.69 (s, 2H), 4.37 (dd, J = 4.5,
1.3 Hz, 2H), 1.79 (bs, 1H), 0.38 (s, 6H); 13C NMR
(101 MHz, CDCl3) d 168.1, 146.6, 140.0, 135.9, 135.0,
134.0, 132.0, 131.0, 129.8, 128.2, 126.9, 123.4, 65.1, 42.0,
ꢀ1.5; IR (KBr) 3518, 2930, 1767, 1705, 1423, 1393, 1337,
1250, 1082, 1038, 993, 935, 841, 816, 779, 745, 727,
530 cmꢀ1. Anal. Calc. for C20H21NO3Si: C, 68.35; H,
6.02. Found: C, 68.41; H, 6.12%.
Following the procedure for 4a, the reaction using hyd-
rosilane 1 (1.25 g, 5.0 mmol) and 5-hexynenitrile (0.46 g,
5.0 mmol) gave 4b (1.09 g, 84%) as a colorless oil, Rf 0.30
1
(hexane–ethyl acetate = 4:1). H NMR (400 MHz, CDCl3)
d 7.53 (d, J = 7.2 Hz, 1H), 7.46 (d, J = 7.2 Hz, 1H), 7.40
(td, J = 7.4, 1.2 Hz, 1H), 7.29 (td, J = 7.4, 1.2 Hz, 1H),
6.06 (dt, J = 18.5, 6.0 Hz, 1H), 5.95 (d, J = 18.4 Hz, 1H),
4.73 (s, 2H), 2.33 (q, J = 7.2 Hz, 4H), 1.79 (quint,
J = 7.2 Hz, 2H), 1.60 (br s, 1H), 0.40 (s, 6H); 13C NMR
(101 MHz, CDCl3) d 146.4, 145.6, 136.2, 135.0, 131.2,
129.7, 127.7, 126.9, 119.5, 65.1, 35.2, 24.0, 16.4, ꢀ1.3; IR
(neat) 3443, 2953, 2249, 1618, 1433, 1250, 1124, 1078,
991, 910, 827, 733 cmꢀ1; MS (EI) m/z (%) 259 (M+, 0.3),
244 (33), 242 (18), 226 (24), 165 (39), 164 (44), 163 (22),
150 (15), 149 (100), 147 (25), 145 (20), 135 (11). Anal. Calc.

596
Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
4.5.6. (E)-3-([2-(Hydroxymethyl)phenyl]dimethylsilyl)-2-
propenyl acetate (4g)
Following the procedure for 4a, the reaction using hyd-
rosilane 1 (2.5 g, 10.0 mmol) and propargyl acetate (0.98 g,
10.0 mmol) gave 4g (0.71 g, 27%) and (E)-[2-(hydroxy-
J = 7.3 Hz, 1H), 6.70 (d, J = 18.8 Hz, 1H), 6.01 (dt,
J = 18.7 Hz, 1H), 5.10 (s, 1H), 5.03 (s, 1H), 4.74 (s, 2H),
1.86 (s, 3H), 1.58 (bs, 1H), 0.45 (s, 6H); 13C NMR
(101 MHz, CDCl3) d 148.1, 146.4, 143.2, 136.5, 135.1,
129.7, 127.9, 127.7, 127.0, 118.0, 65.3, 17.9, ꢀ1.3; IR (neat)
3333, 2955, 1574, 1435, 1248, 1202, 1124, 1078, 988, 893,
835, 748 cmꢀ1. Anal. Calc. for C14H20OSi: C, 72.36; H,
8.67. Found: C, 72.27; H, 8.50%.
methyl)phenyl](3-hydroxypropenyl)dimethylsilane,
a
deacetylated product (1.08 g, 49%). 4g was a colorless oil
and showed Rf 0.18 (hexane–ethyl acetate = 5:1). 1H
NMR (400 MHz, CDCl3) d 7.53 (d, J = 7.3 Hz, 1H), 7.47
(d, J = 7.5 Hz, 1H), 7.41 (td, J = 7.4, 1.1 Hz, 1H), 7.29
(td, J = 7.4, 1.1 Hz, 1H), 6.14 (s, 2H), 4.72 (s, 2H), 4.63
(dd, J = 1.7, 0.7 Hz, 2H), 2.09 (s, 3H), 1.64 (bs, 1H), 0.43
(s, 6H); 13C NMR (101 MHz, CDCl3) d 170.8, 146.5,
141.0, 135.9, 135.1, 131.7, 129.9, 128.1, 127.1, 66.6, 65.3,
20.9, ꢀ1.4; IR (neat) 3427, 2953, 1744, 1624, 1435, 1379,
1236, 1126, 1078, 1028, 839, 785, 750 cmꢀ1; HRMS
(FAB+) Calcd for C14H21O3Si: [M+H]+, 265.1260. Found:
m/z 265.1257. (E)-[2-(Hydroxymethyl)phenyl](3-hydroxyp-
ropenyl)dimethylsilane was a colorless solid (mp = 65.2–
65.7 ꢀC) and showed Rf 0.25 (hexane–ethyl acetate = 2:1).
1H NMR (400 MHz, CDCl3) d 7.54 (dd, J = 7.4, 0.6 Hz,
1H), 7.43 (d, J = 7.5 Hz, 1H), 7.39 (td, J = 7.5, 1.7 Hz,
1H), 7.28 (td, J = 7.3, 1.3 Hz, 1H), 6.26 (dt, J = 18.8,
4.2 Hz, 1H), 6.12 (dt, J = 18.8, 1.3 Hz, 1H), 4.71 (s, 2H),
4.17 (dt, J = 4.0, 0.8 Hz, 2H), 2.19 (bs, 2H), 0.41 (s, 6H);
13C NMR (101 MHz, CDCl3) d 146.5, 146.3, 136.3,
135.0, 129.8, 128.2, 128.1, 127.0, 65.2, 65.1, ꢀ1.4; IR (neat)
3308, 3194, 2949, 2899, 1624, 1429, 1342, 1250, 1200, 1128,
1074, 1026, 1009, 997, 847, 826, 791, 766, 739, 637, 463,
426 cmꢀ1; HRMS (FAB–) Calcd for C12H17O2Si: [M–
H]ꢀ, 221.0998. Found: m/z 221.0998.
4.5.9. (E)-[2-(Hydroxymethyl)phenyl]dimethyl(2-
phenylethenyl)silane (4j)
Following the procedure for 4a, the reaction using hyd-
rosilane 1 (0.55 g, 2.2 mmol) and phenylacetylene (0.20 g,
2.0 mmol) gave 4j (0.45 g, 84%) as a colorless oil, Rf 0.20
(hexane–ethyl acetate = 10:1). 1H NMR (400 MHz,
CDCl3) d 7.62 (dd, J = 7.4, 1.3 Hz, 1H), 7.51–7.41 (m,
4H), 7.37–7.27 (m, 4H), 6.97 (d, J = 19.2 Hz, 1H), 6.67
(d, J = 19.2 Hz, 1H), 4.79 (s, 2H), 1.67 (br s, 1H), 0.52 (s,
6H); 13C NMR (101 MHz, CDCl3) d 146.5, 145.2, 138.0,
136.4, 135.3, 130.0, 128.6, 128.3, 127.9, 127.8, 127.1,
126.5, 65.4, ꢀ1.2; IR (neat) 3444, 3055, 2955, 2359, 1605,
1572, 1495, 1447, 1435, 1248, 1198, 1124, 1076, 1028,
991, 847, 831, 812, 777, 748, 691 cmꢀ1; MS (EI) m/z (%)
268 (M+, 0.5), 253 (11), 235 (15), 165 (14), 164 (29), 163
(19), 150 (15), 149 (100), 147 (13), 137 (35), 135 (10), 105
(11), 104 (25), 103 (12), 91 (24). Anal. Calc. for C17H20OSi:
C, 76.07; H, 7.51. Found: C, 75.73; H, 7.55%.
4.5.10. (E)-[2-(Hydroxymethyl)phenyl]dimethyl(4-octen-
4-yl)silane (4 k)
Following the procedure for 4a, the reaction using hyd-
rosilane
1 (0.55 g, 2.2 mmol) and 4-octyne (0.22 g,
4.5.7. (E)-3-Hydroxy-3-methyl-1-butenyl[2-
(hydroxymethyl)phenyl]dimethylsilane (4h)
2.0 mmol) gave 4 k (0.45 g, 81%) as a colorless oil, Rf
0.25 (hexane–ethyl acetate = 10:1). 1H NMR (400 MHz,
CDCl3) d 7.54 (dd, J = 7.2, 1.2 Hz, 1H), 7.47 (dd,
J = 7.2, 1.2 Hz, 1H), 7.40 (td, J = 7.3, 1.4 Hz, 1H), 7.30–
7.26 (m, 1H), 5.80 (t, J = 7.2 Hz, 1H), 4.70 (s, 2H), 2.12–
2.06 (m, 4H), 1.60 (br s, 1H), 1.38 (m, 2H), 1.28–1.18 (m,
2H), 0.90 (t, J = 7.4 Hz, 3H), 0.83 (t, J = 7.2 Hz, 3H),
0.40 (s, 6H); 13C NMR (101 MHz, CDCl3) d 146.6,
142.8, 140.2, 136.7, 135.3, 129.6, 128.0, 126.9, 65.2, 32.1,
30.8, 23.4, 22.6, 14.5, 14.0, ꢀ1.2; IR (neat) 3319, 2957,
2930, 2870, 1611, 1466, 1435, 1377, 1248, 1124, 1078,
1015, 833, 816, 770, 750, 687 cmꢀ1; MS (EI) m/z (%) 276
(M+, 0.1), 261 (19), 166 (15), 165 (100), 164 (15), 163
(24), 151 (22), 150 (12), 149 (79), 148 (13), 147 (61), 145
(30), 135 (19), 91 (11), 75 (14), 61 (19), 59 (10), 55 (10).
Anal. Calc. for C17H28OSi: C, 73.85; H, 10.21. Found: C,
73.67; H, 10.06%.
The procedure for 4a was successfully applied to the
reaction of hydrosilane 1 (2.5 g, 10.0 mmol) and 2-
methyl-3-butyn-2-ol (0.84 g, 10.0 mmol), and 4h (1.08 g,
43%) was isolated as a colorless oil, Rf 0.25 (hexane–ethyl
1
acetate = 2:1). H NMR (400 MHz, CDCl3) d 7.54 (dd,
J = 7.3, 1.3 Hz, 1H), 7.46 (d, J = 7.1 Hz, 1H), 7.40 (td,
J = 7.3, 1.1 Hz, 1H), 7.29 (td, J = 7.3, 1.3 Hz, 1H), 6.24
(d, J = 18.8 Hz, 1H), 6.04 (d, J = 19.0 Hz, 1H), 4.71 (s,
2H), 2.04 (s, 1H), 1.68 (s, 1H), 1.31 (s, 6H), 0.41 (s, 6H);
13C NMR (101 MHz, CDCl3) d 154.8, 146.4, 136.4,
135.0, 129.7, 128.2, 126.9, 123.6, 71.9, 65.0, 29.1, ꢀ1.3;
IR (neat) 3323, 2964, 1611, 1433, 1375, 1259, 1215, 1022,
826, 750 cmꢀ1. Anal. Calc. for C14H22O2Si: C, 67.15; H,
8.86. Found: C, 67.28; H, 8.88%.
4.5.8. (E)-[2-(Hydroxymethyl)phenyl]dimethyl(3-methyl-
1,3-butadienyl)silane (4i)
4.6. Alternative preparation of (E)-alkenyl[2-
(hydroxymethyl)phenyl]dimethylsilanes using 3
Following the procedure for 4a, the reaction using hyd-
rosilane 1 (2.5 g, 10.0 mmol) and 2-methyl-1-buten-3-yne
(0.66 g, 10.0 mmol) gave 4i (1.31 g, 57%) as a colorless
oil, Rf 0.20 (hexane–ethyl acetate = 10:1). 1H NMR
(400 MHz, CDCl3) d 7.56 (d, J = 7.3 Hz, 1H), 7.47 (d,
J = 7.7 Hz, 1H), 7.41 (td, J = 7.4, 1.1 Hz, 1H), 7.30 (t,
4.6.1. (E)-[2-(Hydroxymethyl)phenyl]dimethyl(1-
octenyl)silane (4a)
A 1.0 M solution of 1-octyne in hexane (0.50 mL,
0.50 mmol) was added dropwise to a mixture of 3

Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
597
(104 mg, 0.50 mmol), t-Bu3P (10% hexane solution,
4.8. Preparation of alkenyl[2-(hydroxymethyl)phenyl]-
dimethylsilanes by the reaction of the Grignard reagents
with 2
10.0 mg, 5.0 lmol), and platinum(0)-1,3-divinyl-1,1,3,3-
tetramethyldisiloxane complex (0.01 M hexane solution,
0.50 mL, 5.0 lmol) at 0 ꢀC. The resulting mixture was
stirred at rt for 4 h, filtered through a Florisil pad, and
concentrated in vacuo. The residue was dissolved in MeOH
(2.5 mL) and water (2.5 mL) and treated with K2CO3
(1.38 g, 10.0 mmol) at 50 ꢀC for 24 h. The mixture was
extracted with diethyl ether, and the combined organic
layers were washed with water and brine and dried
over anhydrous MgSO4; the residue was purified by
flash chromatography on silica gel to give 4a (113 mg,
82%).
4.8.1. [2-(Hydroxymethyl)phenyl]dimethyl(vinyl)silane
(4m)
To a solution of 2 (2.5 g, 15.0 mmol) in THF (30 mL)
was added a 1.0 M solution of vinylmagnesium bromide
in THF (16.5 mL, 16.5 mmol) at 0 ꢀC, and the resulting
mixture was stirred at rt overnight. The mixture was
diluted with diethyl ether, washed with a saturated NH4Cl
aqueous solution, water, and brine, and dried over anhy-
drous MgSO4. After removal of the solvents in vacuo,
the residue was purified by flash chromatography on silica
gel to give 4m (2.3 g, 81%) as a colorless oil, Rf 0.30 (hex-
4.6.2. (E)-5-tert-Butyldimethylsiloxy-1-pentenyl[2-
(hydroxymethyl)phenyl]dimethylsilane (4e)
1
ane–ethyl acetate = 7:1). H NMR (400 MHz, CDCl3) d
The above procedure for 4a was applied to the reaction
of hydrosilane 3 (1.48 g, 7.0 mmol) and 5-tert-butyldimeth-
ylsilyloxy-1-pentyne (1.39 g, 7.0 mmol) to give 4e (2.4 g,
93%) as a colorless oil, Rf 0.40 (hexane–ethyl ace-
tate = 4:1). 1H NMR (400 MHz, CDCl3) d 7.54 (d,
J = 7.3 Hz, 1H), 7.46 (d, J = 7.7 Hz, 1H), 7.40 (td,
J = 7.5, 1.3 Hz, 1H), 7.31–7.26 (m, 1H), 6.15 (dt,
J = 18.5, 6.2 Hz, 1H), 5.86 (d, J = 18.5 Hz, 1H), 4.74 (s,
2H), 3.61 (t, J = 6.5 Hz, 2H), 2.20 (td, J = 6.5, 6.2 Hz,
2H), 1.63 (quint, J = 6.5 Hz, 2H), 1.57 (bs, 1H), 0.87 (s,
9H), 0.39 (s, 6H), 0.04 (s, 6H); 13C NMR (101 MHz,
CDCl3) d 148.8, 146.4, 136.9, 135.1, 129.6, 128.7, 128.0,
127.0, 65.4, 62.5, 33.0, 31.7, 26.0, 18.3, ꢀ1.2, ꢀ5.3; IR
(neat) 3358, 2953, 2930, 2856, 1616, 1472, 1254, 1105,
837, 777 cmꢀ1. Anal. Calc. for C20H36O2Si2: C, 65.87; H,
9.95. Found: C, 65.98; H, 9.65%.
7.56 (dd, J = 7.3, 1.3 Hz, 1H), 7.46 (dd, J = 7.1, 0.7 Hz,
1H), 7.41 (td, J = 7.4, 1.5 Hz, 1H), 7.30 (td, J = 7.3,
1.5 Hz, 1H), 6.39 (dd, J = 20.3, 14.6 Hz, 1H), 6.08 (dd,
J = 14.6, 3.7 Hz, 1H), 5.79 (dd, J = 20.3, 3.7 Hz, 1H),
4.74 (s, 2H), 1.71 (br s, 1H), 0.43 (s, 6H); 13C NMR
(101 MHz, CDCl3) d 146.4, 139.0, 136.2, 135.2, 132.8,
129.8, 128.0, 127.0, 65.3, ꢀ1.6; IR (neat) 3321, 3051,
2957, 1404, 1250, 1078, 1009, 820, 775, 754 cmꢀ1. Anal.
Calc. for C11H16OSi: C, 68.69; H, 8.39. Found: C, 68.43;
H, 8.36%.
4.8.2. (Z)-[2-(Hydroxymethyl)phenyl]dimethyl(propenyl)
silane (4n)
A solution of (Z)-propenylmagnesium bromide in THF
(70 mL) [prepared from (Z)-1-bromopropene (6.0 g,
50 mmol) and Mg turnings (1.71 g, 50 mmol)] [27] was
added to a THF (20 mL) solution of 2 (5.8 g, 35 mmol)
at 0 ꢀC, and the resulting mixture was stirred at rt over-
night. The mixture was diluted with diethyl ether and
filtered to remove unreacted magnesium metal; the filtrate
was washed with a saturated NH4Cl aqueous solution,
water, and brine and dried over anhydrous MgSO4. After
removal of the solvents in vacuo, the residue was purified
by flash chromatography on silica gel to give 4n [6.8 g,
94% as a (Z):(E) = 94:6 mixture as estimated by GC anal-
ysis] as a colorless oil, Rf 0.26 (hexane–ethyl acetate =
7:1). 1H NMR (400 MHz, CDCl3) d 7.59 (dd, J = 7.3,
1.5 Hz, 1H), 7.47 (d, J = 7.6 Hz, 1H), 7.41 (td, J = 7.5,
1.5 Hz, 1H), 7.29 (td, J = 7.3, 1.3 Hz, 1H), 6.52 (dq,
J = 13.9, 7.0 Hz, 1H), 5.76 (dq, J = 13.9, 1.5 Hz, 1H),
4.72 (s, 2H), 1.79 (br d, J = 4.9 Hz, 1H), 1.64 (dd,
J = 6.8, 1.6 Hz, 3H), 0.45 (s, 6H); 13C NMR (101 MHz,
CDCl3) d 146.3, 145.1, 137.5, 134.7, 129.7, 129.3, 128.2,
127.0, 65.4, 19.1, ꢀ0.2; IR (neat) 3319, 3055, 2961,
2910, 1609, 1435, 1248, 1200, 1124, 1078, 1034, 826,
777, 746, 696, 658 cmꢀ1; MS (EI) m/z (%) 206 (M+,
0.1), 191 (12), 173 (29), 166 (10), 165 (62), 164 (37), 163
(18), 150 (15), 149 (100), 148 (11), 147 (39), 145 (48),
135 (16), 131 (14), 105 (11), 91 (11), 75 (43), 61 (19). Anal.
Calc. for C12H18OSi: C, 69.84; H, 8.79. Found: C, 69.82;
H, 8.81%.
4.7. Preparation of (Z)-[2-(hydroxymethyl)phenyl]-
dimethyl(2-phenylethenyl)silane (4l) by ruthenium-
catalyzed hydrosilylation using 1 [10]
A mixture of hydrosilane 1 (1.25 g, 5.0 mmol), phenyl-
acetylene (0.51 g, 5.0 mmol), and RuHCl(CO)[P(i-Pr)3]2
(0.122 g, 0.25 mmol) in CH2Cl2 (25 mL) was stirred at rt
for 3 h before filtration through a silica gel pad and concen-
tration in vacuo. The residue was dissolved in MeOH
(15 mL) and treated with p-toluenesulfonic acid monohy-
drate (18.8 mg, 0.100 mmol) at rt for 9 h. After removal
of the solvents in vacuo, the residue was purified by flash
chromatography on silica gel to give 4l (0.97 g, 72%) as a
colorless oil, Rf 0.20 (hexane–ethyl acetate = 10:1). 1H
NMR (400 MHz, CDCl3) d 7.58 (dd, J = 7.1, 1.1 Hz,
1H), 7.46 (dd, J = 15.0 Hz, 1H), 7.43–7.36 (m, 2H), 7.30
(td, J = 7.1, 2.0 Hz, 1H), 7.17–7.09 (m, 5H), 6.08 (d,
J = 15.2 Hz, 1H), 4.69 (s, 2H), 1.54 (br s, 1H), 0.33 (s,
6H); 13C NMR (101 MHz, CDCl3) d 147.7, 146.1, 138.9,
137.4, 134.6, 131.2, 129.7, 128.2, 127.9, 127.8, 127.6,
127.1, 65.5, ꢀ0.3; IR (neat) 3331, 3055, 2959, 1591, 1568,
1493, 1435, 1250, 1124, 1078, 1028, 814, 758, 698 cmꢀ1
.
Anal. Calc. for C17H20OSi: C, 76.07; H, 7.51. Found: C,
75.80; H, 7.59%.

598
Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
4.8.3. [2-(Hydroxymethyl)phenyl]dimethyl(propen-2-
yl)silane (4o)
(7.5 g, 46 mmol) in THF (50 mL) at 0 ꢀC, and the resulting
mixture was stirred at rt overnight before dilution with
diethyl ether. The mixture was washed with a saturated
NH4Cl aqueous solution, water, and brine and dried over
anhydrous MgSO4. After removal of the solvents in vacuo,
flash chromatography of the residue on neutral aluminium
oxide (activity grade III) gave 4q (7.1 g, 71%) as a colorless
oil, Rf 0.26 (hexane–ethyl acetate = 5:1). 1H NMR
(400 MHz, C6D6) d 7.57 (d, J = 7.3 Hz, 1H), 7.45 (d,
J = 7.7 Hz, 1H), 7.22 (t, J = 7.4 Hz, 1H), 7.13 (d,
J = 7.4 Hz, 1H), 5.41 (s, 1H), 4.63 (d, J = 5.9 Hz, 2H),
1.78 (t, J = 5.9 Hz, 1H), 1.66 (s, 3H), 1.46 (s, 3H), 0.37
(s, 6H); 13C NMR (101 MHz, C6D6) d 153.4, 147.3,
137.5, 134.9, 129.7, 128.0, 127.0, 123.8, 65.3, 29.3, 23.2,
0.0; IR (neat) 3238, 2953, 2907, 1620, 1437, 1371, 1246,
1123, 1076, 1036, 858, 833, 816, 800, 773, 745, 700, 644,
459 cmꢀ1; MS (EI) m/z (%) 220 (M+, 0.04), 205 (10), 165
(28), 164 (32), 163 (17), 150 (14), 149 (100), 148 (10), 147
(25), 145 (30), 135 (10), 105 (10), 75 (27), 61 (16). Anal.
Calc. for C13H20OSi: C, 70.85; H, 9.15. Found: C, 70.83;
H, 9.23%.
To a solution of 2 (7.5 g, 46 mmol) in THF (50 mL) was
added a 0.5 M solution of 2-propenylmagnesium bromide
in THF (100 mL, 50 mmol) at 0 ꢀC, and the resulting mix-
ture was stirred at rt for 9 h. The mixture was diluted with
diethyl ether, washed sequentially with a saturated NH4Cl
aqueous solution, water, and brine, and then dried over
anhydrous MgSO4. After removal of the solvents in vacuo,
the residue was distilled under vacuum to give 4o (8.4 g,
1
89%) as a colorless oil, bp 75 ꢀC (0.4 mmHg). H NMR
(400 MHz, CDCl3) d 7.55 (dd, J = 7.4, 1.2 Hz, 1H), 7.48
(ddd, J = 7.7, 1.3, 0.5 Hz, 1H), 7.42 (td, J = 7.5, 1.5 Hz,
1H), 7.30 (td, J = 7.3, 1.5 Hz, 1H), 5.71 (dq, J = 3.1,
1.6 Hz, 1H), 5.37 (dq, J = 3.1, 1.3 Hz, 1H), 4.72 (s, 2H),
1.92 (br s, 1H), 1.82 (dd, J = 1.6, 1.3 Hz, 3H), 0.44 (s,
6H); 13C NMR (101 MHz, CDCl3) d 147.3, 146.6, 135.4,
135.3, 129.7, 127.9, 126.9, 126.6, 65.1, 22.5, ꢀ2.1; IR (neat)
3329, 2951, 1435, 1248, 1126, 1078, 1034, 924, 835, 818, 775,
754, 696, 662 cmꢀ1; MS (EI) m/z (%) 206 (M+, 0.3), 191
(26), 189 (14), 173 (39), 166 (17), 165 (100), 164 (17), 163
(23), 150 (13), 149 (75), 148 (17), 147 (78), 146 (12), 145
(61), 135 (18), 131 (14), 105 (10), 75 (30). Anal. Calc. for
C12H18OSi: C, 69.84; H, 8.79. Found: C, 69.82; H, 8.56%.
4.9. Cross-coupling of alkenyl[2-(hydroxymethyl)phenyl]-
dimethylsilanes with aryl or alkenyl iodides. A general
procedure
4.8.4. [2-(Hydroxymethyl)phenyl]dimethyl(1-phenyl-
ethenyl)silane (4p)
To a mixture of K2CO3 (0.30 g, 2.2 mmol), a ligand [(2-
furyl)3P, 4.6 mg, 0.020 mmol; 9, 3.7 mg, 0.010 mmol], and
PdCl2 (1.8 mg, 0.010 mmol) in DMSO (2.5 mL) were added
an alkenylsilane (1.10 mmol) and an aryl or alkenyl iodide
(1.00 mmol) sequentially, and the resulting mixture was
stirred at 35 ꢀC. After the time specified in Table 3 and
Eq. (3), the mixture was diluted with diethyl ether, washed
with water and brine, and dried over anhydrous MgSO4.
Concentration in vacuo followed by flash chromatography
on silica gel afforded the corresponding coupling product
in a yield listed in Table 3 and Eq. (3).
To a solution of 1-phenylethenylmagnesium bromide in
THF (18 mL), prepared from a-bromostyrene (4.3 g,
24 mmol) and Mg turnings (0.60 g, 25 mmol) [28], was
added a THF (10 mL) solution of 2 (3.5 g, 21 mmol) at rt,
and the resulting mixture was stirred at rt for 4.5 h. The
mixture was diluted with diethyl ether and filtered to
remove unreacted magnesium; the filtrate was washed with
a saturated NH4Cl aqueous solution, water, and brine and
dried over anhydrous MgSO4. After removal of the solvents
in vacuo, the residue was purified by flash chromatography
on silica gel to give 4p (3.2 g, 56%) as a colorless oil, Rf 0.28
1
(hexane–ethyl acetate = 5:1). H NMR (400 MHz, CDCl3)
4.9.1. (E)-1-(4-Cyanophenyl)-1-octene (6aa)
d 7.61 (dd, J = 7.4, 1.3 Hz, 1H), 7.48 (dd, J = 7.6, 0.8 Hz,
1H), 7.43 (td, J = 7.4, 1.3 Hz, 1H), 7.31 (td, J = 7.3,
1.5 Hz, 1H), 7.25–7.15 (m, 3H), 7.13–7.08 (m, 2H), 6.04
(d, J = 1.4 Hz, 1H), 5.71 (d, J = 1.4 Hz, 1H), 4.73 (s, 2H),
1.55 (br s, 1H), 0.48 (s, 6H); 13C NMR (101 MHz, CDCl3)
d 152.0, 146.5, 143.6, 135.8, 135.3, 129.9, 128.8, 128.2,
128.1, 127.1, 126.72, 126.65, 65.2, ꢀ0.8; IR (neat) 3339,
3055, 2955, 1597, 1489, 1439, 1408, 1250, 1200, 1124,
1078, 1028, 934, 831, 812, 781, 754, 708, 633 cmꢀ1; MS
(EI) m/z (%) 268 (M+, 0.2), 253 (6), 235 (25), 209 (10),
166 (15), 165 (100), 163 (22), 149 (32), 148 (11), 147 (60),
145 (23), 137 (22), 135 (12), 104 (20). Anal. Calc. for
C17H20OSi: C, 76.07; H, 7.51. Found: C, 76.31; H, 7.48%.
A colorless oil, Rf 0.31 (hexane–ethyl acetate = 20:1). 1H
NMR (400 MHz, CDCl3) d 7.55 (d, J = 8.4 Hz, 2H), 7.39
(d, J = 8.4 Hz, 2H), 6.38–6.35 (m, 2H), 2.24–2.20 (m,
2H), 1.50–1.42 (m, 2H), 1.40–1.25 (m, 6H), 0.92–0.86 (m,
3H); 13C NMR (101 MHz, CDCl3) d 142.4, 135.5, 132.2,
128.3, 126.3, 119.1, 109.8, 33.1, 31.6, 28.9, 28.8, 22.5,
14.0; IR (neat) 2955, 2928, 2855, 2226, 1649, 1605, 1502,
1466, 1412, 1175, 966, 856, 733, 552 cmꢀ1; MS (EI) m/z
(%) 213 (M+, 18), 143 (11), 142 (34), 130 (19), 129 (100),
116 (14), 115 (11). Anal. Calc. for C15H19N: C, 84.46; H,
8.98. Found: C, 84.37; H, 8.96%.
4.9.2. (E)-1-(4-Ethoxycarbonylphenyl)-1-octene (6ab)
A colorless oil, Rf 0.40 (hexane–ethyl acetate = 20:1). 1H
NMR (400 MHz, CDCl3) d 7.96 (d, J = 8.4 Hz, 2H), 7.38
(d, J = 7.0 Hz, 2H), 6.45–6.32 (m, 2H), 4.37 (q,
J = 7.2 Hz, 2H), 2.23 (q, J = 7.2 Hz, 2H), 1.53–1.28 (m,
11H), 0.94–0.86 (m, 3H); 13C NMR (101 MHz, CDCl3) d
4.8.5. [2-(Hydroxymethyl)phenyl]dimethyl(2-
methylpropenyl)silane (4q)
A 0.5 M THF solution of 2-methylpropenylmagnesium
bromide (100 mL, 50 mmol) was added to a solution of 2

Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
599
166.5, 142.4, 134.2, 129.8, 129.0, 128.5, 125.7, 60.8, 33.2,
31.7, 29.1, 28.9, 22.6, 14.3, 14.1; IR (neat) 2957, 2928,
2855, 1715, 1607, 1466, 1412, 1366, 1275, 1177, 1107,
1020, 968, 957, 864, 762, 696 cmꢀ1; MS (EI) m/z (%) 261
(M++1, 14), 260 (M+, 76), 215 (37), 177 (16), 176 (100),
161 (11), 148 (45), 145 (23), 132 (10), 131 (55), 129 (16),
128 (13), 118 (10), 117 (86), 116 (23), 115 (49), 91 (18).
Anal. Calc. for C17H24O2: C, 78.42; H, 9.29. Found: C,
78.45; H, 9.41%.
13C NMR (101 MHz, CDCl3) d 136.4, 132.2, 132.0,
128.54, 128.49, 127.1, 33.0, 31.7, 29.2, 28.9, 22.6, 14.1; IR
(neat) 2957, 2926, 2855, 1709, 1491, 1466, 1404, 1092,
1013, 964, 845, 820, 802, 735 cmꢀ1; MS (EI) m/z (%) 224
(M++2, 15), 222 (M+, 44), 153 (29), 152 (12), 151 (88),
140 (31), 139 (10), 138 (100), 129 (10), 125 (17), 117 (11),
116 (36), 115 (46); HRMS (EI) Calcd for C14H19Cl: M+,
222.1175. Found: m/z 222.1172.
4.9.7. (E)-1-(4-Methoxyphenyl)-1-octene (6ag)
4.9.3. (E)-1-(4-Acetylphenyl)-1-octene (6ac)
A colorless oil, Rf 0.36 (hexane–ethyl acetate = 50:1). 1H
NMR (400 MHz, CDCl3) d 7.28 (d, J = 8.7 Hz, 2H), 6.84
(d, J = 8.7 Hz, 2H), 6.33 (d, J = 15.7 Hz, 1H), 6.09 (dt,
J = 15.7, 7.0 Hz, 1H), 3.81 (s, 3H), 2.19 (q, J = 7.5 Hz,
2H), 1.50–1.42 (m, 2H), 1.40–1.26 (m, 6H), 0.93–0.88 (m,
3H); 13C NMR (101 MHz, CDCl3) d 158.6, 130.8, 129.1,
129.0, 126.9, 113.9, 55.2, 33.0, 31.8, 29.5, 28.9, 22.6, 14.1;
IR (neat) 2955, 2926, 2855, 1609, 1510, 1466, 1248, 1175,
1038, 964, 841 cmꢀ1; MS (EI) m/z (%) 218 (M+, 39), 148
(12), 147 (100), 134 (14), 121 (15), 91 (10). Anal. Calc.
for C15H22O: C, 82.52; H, 10.16. Found: C, 82.52; H,
9.98%.
A colorless oil, Rf 0.30 (hexane–ethyl acetate = 20:1). 1H
NMR (400 MHz, CDCl3) d 7.88 (d, J = 8.4 Hz, 2H), 7.39
(d, J = 8.4 Hz, 2H), 6.43–6.33 (m, 2H), 2.57 (s, 3H), 2.23
(q, J = 6.4 Hz, 2H), 1.52–1.42 (m, 2H), 1.40–1.25 (m,
6H), 0.92–0.86 (m, 3H); 13C NMR (101 MHz, CDCl3) d
197.5, 142.6, 135.3, 134.5, 128.8, 128.7, 125.8, 33.1, 31.7,
29.1, 28.9, 26.5, 22.6, 14.0; IR (neat) 2957, 2926, 2855,
1682, 1603, 1410, 1358, 1267, 1180, 966, 592 cmꢀ1; MS
(EI) m/z (%) 231 (M++1, 12), 230 (M+, 73), 216 (11), 215
(72), 148 (10), 147 (15), 146 (56), 145 (11), 134 (11), 131
(100), 128 (11), 117 (19), 116 (12), 115 (36). Anal. Calc.
for C16H22O: C, 83.43; H, 9.63. Found: C, 83.72; H, 9.74%.
4.9.8. (E)-1-[3-(tert-Butyldimethylsiloxymethyl)phenyl]-1-
octene (6ah)
4.9.4. (E)-1-(4-Formylphenyl)-1-octene (6ad)
A colorless oil, Rf 0.30 (hexane–ethyl acetate = 30:1). 1H
NMR (400 MHz, CDCl3) d 9.96 (s, 1H), 7.80 (d,
J = 8.4 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 6.64–6.42 (m,
2H), 2.28–2.22 (m, 2H), 1.53–1.44 (m, 2H), 1.40–1.25 (m,
6H), 0.92–0.86 (m, 3H); 13C NMR (101 MHz, CDCl3) d
191.7, 144.1, 135.4, 134.8, 130.1, 128.9, 126.3, 33.2, 31.7,
29.0, 28.9, 22.6, 14.1; IR (neat) 2955, 2926, 2855, 1697,
1603, 1568, 1304, 1213, 1167, 966, 851, 802 cmꢀ1; MS
(EI) m/z (%) 216 (M+, 43), 133 (14), 132 (100), 131 (39),
117 (62), 116 (11), 115 (29), 91 (19). Anal. Calc. for
C15H20O: C, 83.28; H, 9.32. Found: C, 83.40; H, 9.37%.
A colorless oil, Rf 0.35 (hexane–ethyl acetate = 50:1). 1H
NMR (400 MHz, CDCl3) d 7.30 (s, 1H), 7.25–7.13 (m, 3H),
6.37 (d, J = 15.7 Hz, 1H), 6.22 (dt, J = 15.7, 6.9 Hz, 1H),
4.72 (s, 2H), 2.20 (q, J = 7.7 Hz, 2H), 1.50–1.42 (m, 2H),
1.38–1.26 (m, 6H), 0.95 (s, 9H), 0.39 (t, J = 6.9 Hz, 3H),
0.10 (s, 6H); 13C NMR (101 MHz, CDCl3) d 141.5,
137.8, 131.2, 129.7, 128.3, 124.49, 124.47, 123.5, 64.9,
33.0, 31.7, 29.3, 28.9, 26.0, 22.6, 18.4, 14.1, ꢀ5.2; IR (neat)
2955, 2928, 2856, 1462, 1256, 1105, 1080, 962, 837,
777 cmꢀ1; MS (EI) m/z (%) 332 (M+, 2), 276 (27), 275
(100), 245 (16), 201 (34). Anal. Calc. for C21H36OSi: C,
75.84; H, 10.91. Found: C, 75.97; H, 11.13%.
4.9.5. (E)-1-(4-Nitrophenyl)-1-octene (6ae)
A colorless oil, Rf 0.17 (hexane–ethyl acetate = 30:1). 1H
NMR (400 MHz, CDCl3) d 8.14 (d, J = 8.8 Hz, 2H), 7.44
(d, J = 8.8 Hz, 2H), 6.46–6.42 (m, 2H), 2.30–2.20 (m,
2H), 1.54–1.42 (m, 2H), 1.40–1.24 (m, 6H), 0.93–0.87 (m,
3H); 13C NMR (101 MHz, CDCl3) d 146.3, 144.4, 136.7,
128.0, 126.3, 123.9, 33.2, 31.6, 28.91, 28.87, 22.6, 14.0; IR
(neat) 2955, 2928, 2855, 1649, 1597, 1518, 1466, 1342,
1109, 968, 955, 860, 824, 745, 689 cmꢀ1; MS (EI) m/z (%)
234 (M++1, 11), 233 (M+, 67), 151 (12), 150 (40), 149
(100), 137 (29), 129 (13), 128 (17), 119 (22), 117 (19), 116
(79), 115 (70), 103 (13), 91 (11), 55 (11); HRMS (FAB+)
Calcd for C14H20NO2: [M+H]+, 234.1494. Found: m/z
234.1497.
4.9.9. (E)-1-[3-(Hydroxymethyl)phenyl]-1-octene (6ai)
1
A colorless oil, Rf 0.30 (hexane–ethyl acetate = 5:1). H
NMR (400 MHz, CDCl3) d 7.36 (s, 1H), 7.32–7.27 (m, 2H),
7.21–7.18 (m, 1H), 6.38 (d, J = 15.6 Hz, 1H), 6.26 (dt,
J = 16.0, 6.8 Hz, 1H), 4.68 (s, 2H), 2.21 (q, J = 7.2 Hz,
2H), 1.62 (br s, 1H), 1.51–1.42 (m, 2H), 1.40–1.26 (m,
6H), 0.93–0.87 (m, 3H); 13C NMR (101 MHz, CDCl3) d
141.0, 138.3, 131.7, 129.4, 128.7, 125.35, 125.32, 124.4,
65.4, 33.0, 31.7, 29.3, 28.9, 22.6, 14.1; IR (neat) 3329,
2955, 2926, 2855, 1466, 1433, 1020, 962, 775, 733,
696 cmꢀ1; MS (EI) m/z (%) 218 (M+, 36), 134 (42), 132
(16), 131 (16), 129 (24), 128 (12), 118 (14), 117 (100), 115
(22), 105 (10), 91 (20). Anal. Calc. for C15H22O: C, 82.52;
H, 10.16. Found: C, 82.63; H, 10.40%.
4.9.6. (E)-1-(4-Chlorophenyl)-1-octene (6af)
1
A colorless oil, Rf 0.60 (hexane). H NMR (400 MHz,
4.9.10. (E)-1-(2-Methylphenyl)-1-octene (6aj)
1
CDCl3) d 7.26 (s, 4H), 6.33 (dt, J = 15.5, 1.2 Hz, 1H),
6.21 (dt, J = 15.5, 6.8 Hz, 1H), 2.20 (q, J = 6.8 Hz, 2H),
1.52–1.42 (m, 2H), 1.40–1.23 (m, 6H), 0.94–0.88 (m, 3H);
A colorless oil, Rf 0.71 (hexane). H NMR (400 MHz,
CDCl3) d 7.41 (d, J = 7.2 Hz, 1H), 7.19–7.10 (m, 3H),
6.57 (d, J = 15.6 Hz, 1H), 6.10 (dt, J = 15.6, 6.8 Hz, 1H),

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Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
2.34 (s, 3H), 2.23 (q, J = 7.2 Hz, 2H), 1.54–1.42 (m, 2H),
1.40–1.26 (m, 6H), 0.92–0.88 (m, 3H); 13C NMR
(101 MHz, CDCl3) d 137.1, 134.8, 132.6, 130.1, 127.5,
126.7, 126.0, 125.4, 33.3, 31.7, 29.4, 28.9, 22.6, 19.8, 14.1;
IR (neat) 3020, 2957, 2926, 2855, 1485, 1460, 1377, 962,
745 cmꢀ1; MS (EI) m/z (%) 202 (M+, 42), 132 (13), 131
(100), 129 (12), 118 (51), 117 (18), 116 (17), 115 (18), 105
(16), 91 (15). Anal. Calc. for C15H22: C, 89.04; H, 10.96.
Found: C, 88.97; H, 11.18%.
(d, J = 8.4 Hz, 2H), 6.50 (d, J = 16.0 Hz, 1H), 6.31–6.22
(m, 1H), 4.36 (q, J = 7.2 Hz, 2H), 2.44–2.38 (m, 4H),
1.86 (quint, J = 7.2 Hz, 2H), 1.39 (t, J = 7.2 Hz, 3H);
13C NMR (101 MHz, CDCl3) d 166.4, 141.4, 131.2,
130.4, 129.9, 129.1, 125.9, 119.4, 60.9, 31.7, 24.8, 16.5,
14.3; IR (neat) 2984, 2937, 2907, 2243, 1711, 1607,
1458, 1437, 1414, 1366, 1271, 1180, 1126, 1109, 1092,
1024, 968, 955, 768, 750, 694 cmꢀ1; MS (EI) m/z (%)
244 (M++1, 14), 243 (M+, 81), 199 (15), 198 (100), 197
(16), 196 (19), 170 (12), 157 (14), 145 (15), 130 (14), 129
(43), 128 (22), 117 (57), 116 (16), 115 (40); HRMS (EI)
Calcd for C15H17NO2: M+, 243.1259. Found: m/z
243.1259.
4.9.11. (E)-1-(1-Naphthyl)-1-octene (6ak)
1
A colorless oil, Rf 0.50 (hexane). H NMR (400 MHz,
CDCl3) d 8.13 (d, J = 7.6 Hz, 1H), 7.84 (d, J = 7.2 Hz,
1H), 7.74 (d, J = 8.0 Hz, 1H), 7.58–7.40 (m, 4H), 7.11 (d,
J = 15.2 Hz, 1H), 6.24 (dt, J = 16.0, 7.2 Hz, 1H), 2.33 (q,
J = 7.6 Hz, 2H), 1.60–1.52 (m, 2H), 1.46–1.32 (m, 6H),
0.94–0.88 (m, 3H); 13C NMR (101 MHz, CDCl3) d 135.8,
134.6, 133.6, 131.1, 128.4, 127.1, 126.8, 125.74, 125.65,
125.58, 124.0, 123.5, 33.5, 31.8, 29.4, 29.0, 22.7, 14.1; IR
(neat) 3059, 3044, 2955, 2926, 2855, 1591, 1508, 1466,
1394, 964, 775, 727 cmꢀ1; MS (EI) m/z (%) 238 (M+, 44),
168 (17), 167 (100), 166 (15), 165 (35), 154 (21), 153 (24),
152 (22), 141 (13). Anal. Calc. for C18H22: C, 90.70; H,
9.30. Found: C, 90.61; H, 9.32%.
4.9.15. Methyl (E)-6-(4-ethoxycarbonylphenyl)-5-
hexenoate (6cb)
A colorless oil, Rf 0.32 (hexane–ethyl acetate = 5:1).
1H NMR (400 MHz, CDCl3) d 7.97 (d, J = 8.4 Hz,
2H), 7.38 (d, J = 8.4 Hz, 2H), 6.44 (d, J = 15.8 Hz,
1H), 6.31 (dt, J = 15.8, 6.8 Hz, 1H), 4.37 (q,
J = 7.1 Hz, 2H), 3.66 (s, 3H), 2.37 (t, J = 6.8 Hz, 2H),
2.29 (q, J = 6.8 Hz, 2H), 1.84 (quint, J = 6.8 Hz, 2H),
1.39 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 173.9, 166.5, 141.9, 132.4, 130.1, 129.8, 128.8, 125.8,
60.8, 51.5, 33.4, 32.4, 24.3, 14.3; IR (neat) 2982, 2951,
1736, 1717, 1607, 1275, 1178, 1107, 1020, 970, 860,
4.9.12. (E)-1-(3-Pyridyl)-1-octene (6al)
A colorless oil, Rf 0.35 (hexane–ethyl acetate = 5:1). H
1
760 cmꢀ1
;
HRMS (EI) Calcd for C16H20O4: M+,
NMR (400 MHz, CDCl3) d 8.56 (br s, 1H), 8.42 (br d,
J = 3.7 Hz, 1H), 7.65 (d, J = 7.9 Hz, 1H), 7.22 (dd,
J = 7.8, 4.8 Hz, 1H), 6.38–6.26 (m, 2H), 2.26–2.20 (m, 2H),
1.52–1.43 (m, 2H), 1.40–1.26 (m, 6H), 0.92–0.86 (m, 3H);
13C NMR (101 MHz, CDCl3) d 147.8, 147.7, 133.8, 133.5,
132.5, 126.1, 123.4, 33.1, 31.7, 29.1, 28.9, 22.6, 14.1; IR (neat)
3024, 2955, 2926, 2855, 2359, 2341, 1653, 1568, 1466, 1414,
1022, 964, 708 cmꢀ1; MS (EI) m/z (%) 189 (M+, 46), 146
(10), 132 (10), 130 (10), 119 (14), 118 (87), 117 (37), 106
(27), 105 (100), 93 (14), 91 (15). Anal. Calc. for C13H19N:
C, 82.48; H, 10.12. Found: C, 82.20; H, 10.06%.
276.1362. Found: m/z 276.1359.
4.9.16. (E)-5-Chloro-1-(4-ethoxycarbonylphenyl)-1-
pentene (6db)
A colorless oil, Rf 0.25 (hexane–ethyl acetate = 10:1). 1H
NMR (400 MHz, CDCl3) d 7.97 (d, J = 8.3 Hz, 2H), 7.39
(d, J = 8.3 Hz, 2H), 6.48 (d, J = 15.9 Hz, 1H), 6.31 (dt,
J = 15.9, 6.3 Hz, 1H), 4.37 (q, J = 7.1 Hz, 2H), 3.59 (t,
J = 6.3 Hz, 2H), 2.42 (q, J = 6.3 Hz, 2H), 1.97 (quint,
J = 6.3 Hz, 2H), 1.39 (t, J = 7.1 Hz, 3H); 13C NMR
(101 MHz, CDCl3) d 166.4, 141.8, 131.5, 130.5, 129.9,
129.0, 125.8, 60.9, 44.2, 31.8, 30.1, 14.3; IR (neat) 2982,
2959, 2937, 1715, 1607, 1277, 1178, 1107, 1020, 970,
758 cmꢀ1. Anal. Calc. for C14H17ClO2: C, 66.53; H, 6.78.
Found: C, 66.61; H, 6.71%.
4.9.13. (E)-1-(2-Thienyl)-1-octene (6am)
1
A colorless oil, Rf 0.70 (hexane). H NMR (400 MHz,
CDCl3) d 7.08 (d, J = 5.2 Hz, 1H), 6.95–6.91 (m, 1H),
6.86 (d, J = 3.2 Hz, 1H), 6.50 (d, J = 15.6 Hz, 1H), 6.07
(dt, J = 15.6, 6.8 Hz, 1H), 2.17 (q, J = 7.2 Hz, 2H), 1.52–
1.41 (m, 2H), 1.40–1.24 (m, 6H), 0.94–0.86 (m, 3H); 13C
NMR (101 MHz, CDCl3) d 131.3, 127.2, 124.1, 123.0,
122.9, 108.2, 32.9, 31.7, 29.2, 28.9, 22.6, 14.1; IR (neat)
2955, 2926, 2855, 1724, 1686, 1676, 1466, 1437, 1420,
1377, 1211, 1042, 953, 853, 723, 692 cmꢀ1; MS (EI) m/z
(%) 194 (M+, 41), 147 (10), 124 (12), 123 (100), 110 (46),
97 (14), 73 (18); HRMS (EI) Calcd for C12H18S: M+,
194.1129. Found: m/z 194.1126.
4.9.17. (E)-5-tert-Butyldimethylsiloxy-1-(4-
ethoxycarbonylphenyl)-1-pentene (6eb)
A colorless oil, Rf 0.23 (hexane–ethyl acetate = 20:1). 1H
NMR (400 MHz, CDCl3) d 7.96 (d, J = 8.3 Hz, 2H), 7.38
(d, J = 8.3 Hz, 2H), 6.43 (d, J = 15.9 Hz, 1H), 6.31 (dt,
J = 15.9, 6.3 Hz, 1H), 4.36 (q, J = 7.1 Hz, 2H), 3.67 (t,
J = 6.3 Hz, 2H), 2.31 (q, J = 7.0 Hz, 2H), 1.74–1.65 (m,
2H), 1.39 (t, J = 7.1 Hz, 3H), 0.91 (s, 9H), 0.06 (s, 6H);
13C NMR (101 MHz, CDCl3) d 166.6, 142.3, 133.5,
129.9, 129.4, 128.7, 125.7, 62.4, 60.8, 32.2, 29.5, 26.0,
18.4, 14.4, ꢀ5.3; IR (neat) 2955, 2930, 2895, 2856, 1719,
1607, 1275, 1177, 1105, 1020, 968, 837, 775 cmꢀ1; HRMS
(CI) Calcd for C20H33O3Si: [M+H]+, 349.2199. Found:
m/z 349.2193.
4.9.14. (E)-6-(4-Ethoxycarbonylphenyl)-5-hexenenitrile
(6bb)
1
A colorless oil, Rf 0.30 (hexane–ethyl acetate = 5:1). H
NMR (400 MHz, CDCl3) d 7.98 (d, J = 8.4 Hz, 2H), 7.39

Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
601
4.9.18. (E)-N-[3-(4-Ethoxycarbonylphenyl)-2-
propenyl]phthalimide (6fb)
4.9.22. (E)-4-Ethoxycarbonylstilbene (6jb)
A colorless solid (mp 106.0–106.5 ꢀC), Rf 0.30 (hexane–
1
A colorless solid (mp = 124.0–125.0 ꢀC), Rf 0.72 (hex-
ethyl acetate = 20:1). H NMR (400 MHz, CDCl3) d 8.03
1
ane–ethyl acetate = 3:1). H NMR (400 MHz, CDCl3) d
(d, J = 8.4 Hz, 2H), 7.58–7.52 (m, 4H), 7.41–7.36 (m, 2H),
7.32–7.27 (m, 1H), 7.22 (d, J = 16.4 Hz, 1H), 7.13 (d,
J = 16.4 Hz, 1H), 4.39 (q, J = 7.1 Hz, 2H), 1.41 (t,
J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) d 166.4,
141.7, 136.7, 131.1, 130.0, 129.2, 128.8, 128.2, 127.6,
126.8, 126.3, 60.9, 14.4; IR (KBr) 2976, 1705, 1607,
1367, 1283, 1180, 1130, 1109, 1024, 976, 770, 696,
527 cmꢀ1; MS (EI) m/z (%) 253 (M++1, 20), 252 (M+,
100), 208 (12), 207 (65), 180 (10), 179 (54), 178 (57). Anal.
Calc. for C17H16O2: C, 80.93; H, 6.39. Found: C, 81.18;
H, 6.27%.
7.96 (d, J = 8.3 Hz, 2H), 7.90–7.80 (m, 2H), 7.76–7.66
(m, 2H), 7.40 (d, J = 8.3 Hz, 2H), 6.68 (d, J = 15.9 Hz,
1H), 6.37 (dt, J = 15.9, 6.4 Hz, 1H), 4.48 (d, J =
6.4 Hz, 2H), 4.36 (q, J = 7.1 Hz, 2H), 1.38 (t,
J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) d 167.8,
166.3, 140.6, 134.1, 132.7, 132.1, 129.8, 129.7, 126.4,
125.4, 123.4, 60.9, 39.5, 14.3; IR (KBr) 2968, 1773,
1728, 1703, 1470, 1427, 1396, 1367, 1294, 1265, 1180,
1109, 980, 955, 746, 727, 710, 530 cmꢀ1. Anal. Calc.
for C20H17NO4: C, 71.63; H, 5.11. Found: C, 71.58; H,
5.18%.
4.9.23. (E)-4-(4-Ethoxycarbonylphenyl)-4-octene (6kb)
A colorless oil, Rf 0.40 (hexane–ethyl acetate = 30:1).
1H NMR (400 MHz, CDCl3) d 7.97 (d, J = 8.6 Hz,
2H), 7.39 (d, J = 8.8 Hz, 2H), 5.76 (t, J = 7.3 Hz, 1H),
4.37 (q, J = 7.1 Hz, 2H), 2.49 (t, J = 7.5 Hz, 2H), 2.19
(q, J = 7.3 Hz, 2H), 1.53–1.42 (m, 2H), 1.41–1.32 (m,
5H), 0.97 (t, J = 7.3 Hz, 3H), 0.88 (t, J = 7.3 Hz, 3H);
13C NMR (101 MHz, CDCl3) d 166.6, 148.0, 139.4,
131.1, 129.5, 128.4, 126.2, 60.8, 31.4, 30.7, 22.9, 21.8,
14.4, 14.0, 13.9; IR (neat) 2959, 2932, 2872, 1720,
1607, 1462, 1408, 1366, 1273, 1180, 1107, 1020, 858,
772, 706 cmꢀ1; MS (EI) m/z (%) 261 (M++1, 15), 260
(M+, 79), 231 (16), 217 (44), 215 (31), 190 (21), 189
(15), 187 (51), 173 (30), 159 (16), 157 (13), 146 (13),
145 (100), 143 (17), 131 (35), 130 (15), 129 (46), 128
(32), 127 (10), 117 (63), 116 (11), 115 (31), 91 (19). Anal.
Calc. for C17H24O2: C, 78.42; H, 9.29. Found: C, 78.28;
H, 9.14%.
4.9.19. (E)-3-(4-Ethoxycarbonylphenyl)-2-propenyl acetate
(6gb)
1
A colorless oil, Rf 0.31 (hexane–ethyl acetate = 5:1). H
NMR (400 MHz, CDCl3) d 8.00 (d, J = 8.3 Hz, 2H), 7.44
(d, J = 8.3 Hz, 2H), 6.68 (d, J = 15.9 Hz, 1H), 6.39 (dt,
J = 15.9, 6.2 Hz, 1H), 4.75 (d, J = 6.2 Hz, 2H), 4.37 (q,
J = 7.1 Hz, 2H), 2.11 (s, 3H), 1.39 (t, J = 7.1 Hz, 3H);
13C NMR (101 MHz, CDCl3) d 170.7, 166.3, 140.5,
132.8, 129.9, 129.8, 126.4, 125.8, 64.7, 61.0, 20.9, 14.3; IR
(neat) 2982, 2937, 1742, 1715, 1609, 1366, 1277, 1229,
1178, 1107, 1024, 970, 866, 760, 698 cmꢀ1. Anal. Calc.
for C14H16O4: C, 67.73; H, 6.50. Found: C, 67.88; H,
6.44%.
4.9.20. (E)-4-(4-Ethoxycarbonylphenyl)-2-methyl-3-buten-
2-ol (6hb)
A colorless solid (mp = 38.0–38.8 ꢀC), Rf 0.29 (hexane–
ethyl acetate = 2:1). 1H NMR (400 MHz, CDCl3) d 7.99 (d,
J = 8.3 Hz, 2H), 7.43 (d, J = 8.3 Hz, 2H), 6.64 (d,
J = 16.1 Hz, 1H), 6.46 (d, J = 16.1 Hz, 1H), 4.37 (q,
J = 7.1 Hz, 2H), 1.57 (br s, 1H), 1.44 (s, 6H), 1.39 (t,
J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) d 166.4,
141.4, 140.0, 129.9, 129.2, 126.2, 125.6, 71.1, 60.9, 29.9,
14.3; IR (KBr) 3311, 2980, 1712, 1609, 1366, 1281, 1180,
1146, 1111, 1020, 974, 903, 872, 764, 698 cmꢀ1; HRMS
(EI) Calcd for C14H18O3: M+, 234.1256 Found: m/z
234.1248.
4.9.24. (Z)-4-Ethoxycarbonylstilbene (6lb)
A colorless oil, Rf 0.33 (hexane–ethyl acetate = 20:1). 1H
NMR (400 MHz, CDCl3) d 7.89 (d, J = 8.4 Hz, 2H), 7.30
(d, J = 8.4 Hz, 2H), 7.24–7.19 (m, 5H), 6.71 (d,
J = 12.4 Hz, 1H), 6.60 (d, J = 12.4 Hz, 1H), 4.36 (q,
J = 7.1 Hz, 2H), 1.38 (t, J = 7.1 Hz, 3H); 13C NMR
(101 MHz, CDCl3) d 166.4, 142.0, 136.7, 132.1, 109.5,
129.3, 128.9, 128.83, 128.79, 128.3, 127.5, 60.9, 14.3; IR
(neat) 2980, 1717, 1607, 1366, 1275, 1178, 1103, 1020,
781, 714, 698 cmꢀ1. Anal. Calc. for C17H16O2: C, 80.93;
H, 6.39. Found: C, 80.70; H, 6.27%.
4.9.21. (E)-1-(4-Ethoxycarbonylphenyl)-3-methyl-1,3-
butadiene (6ib)
A colorless solid (mp = 43.5–44.5 ꢀC), Rf 0.23 (hexane–
4.9.25. Ethyl 4-vinylbenzoate (6mb) [29]
1
ethyl acetate = 20:1). H NMR (400 MHz, CDCl3) d 7.99
A colorless oil, Rf 0.30 (hexane–ethyl acetate = 30:1). 1H
NMR (400 MHz, CDCl3) d 8.00 (d, J = 8.4 Hz, 2H), 7.46
(d, J = 8.4 Hz, 2H), 6.75 (dd, J = 17.6, 11.2 Hz, 1H), 5.86
(d, J = 17.2 Hz, 1H), 5.38 (d, J = 10.8 Hz, 1H), 4.37 (q,
J = 7.2 Hz, 2H), 1.40 (t, J = 7.2 Hz, 3H).
(d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 6.97 (d,
J = 16.1 Hz, 1H), 6.55 (d, J = 16.1 Hz, 1H), 5.19 (s, 1H),
5.15 (s, 1H), 4.37 (q, J = 7.1 Hz, 2H), 1.98 (s, 3H), 1.40
(t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) d
166.4, 141.80, 141.77, 134.0, 129.9, 129.1, 127.7, 126.2,
118.9, 60.9, 18.5, 14.3; IR (KBr) 2984, 1705, 1605, 1288,
1263, 1184, 1130, 1109, 1022, 986, 880, 772, 708,
536 cmꢀ1. Anal. Calc. for C14H16O2: C, 77.75; H, 7.46.
Found: C, 77.48; H, 7.39%.
4.9.26. 1-(4-Ethoxycarbonylphenyl)propene
[(Z):(E) = 94:6] (6nb)
A colorless oil, Rf 0.33 (hexane–ethyl acetate = 20:1).
[Spectra of (Z)-isomer] 1H NMR (400 MHz, CDCl3) d

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Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
8.01 (dd, J = 8.4 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 6.46
(dd, J = 11.8, 1.8 Hz, 1H), 5.90 (dq, J = 11.8, 7.2 Hz,
1H), 4.38 (q, J = 7.2 Hz, 2H), 1.91 (dd, J = 7.2, 1.8 Hz,
3H), 1.40 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 166.5, 142.2, 129.4, 129.1, 129.0, 128.7, 128.3, 60.8, 14.8,
14.3; IR (neat) 2980, 1715, 1609, 1367, 1310, 1277, 1178,
1105, 1020, 866, 773, 733, 721, 700 cmꢀ1; MS (EI) m/z
(%) 190 (M+, 50), 162 (12), 146 (13), 145 (100), 117 (20),
115 (25), 91 (10). Anal. Calc. for C12H14O2: C, 75.76; H,
7.42. Found: C, 75.90; H, 7.44%.
2H), 1.93 (s, 3H), 1.88 (s, 3H), 1.39 (t, J = 7.1 Hz, 3H);
13C NMR (101 MHz, CDCl3) d 166.6, 143.3, 137.9,
129.3, 128.5, 127.7, 124.6, 60.8, 27.1, 19.6, 14.3; IR (neat)
2980, 1715, 1607, 1410, 1366, 1275, 1178, 1103, 1020,
878, 760, 706 cmꢀ1; MS (EI) m/z (%) 205 (M++1, 11),
204 (M+, 78), 160 (14), 159 (100), 131 (32), 116 (12), 115
(19), 91 (16). Anal. Calc. for C13H16O2: C, 76.44; H,
7.90. Found: C, 76.24; H, 7.99%.
4.9.31. (5E,7E)-Tetradeca-5,7-dienenitrile (8ba)
1
A colorless oil, Rf 0.42 (hexane–ethyl acetate = 5:1). H
4.9.27. 2-(4-Ethoxycarbonylphenyl)propene (6ob)
NMR (400 MHz, CDCl3) d 6.11–5.94 (m, 2H), 5.63 (dt,
J = 14.6, 7.0 Hz, 1H), 5.46 (dt, J = 14.8, 7.0 Hz, 1H),
2.34 (t, J = 7.1 Hz, 2H), 2.22 (q, J = 7.1 Hz, 2H), 2.06
(dt, J = 7.1, 7.0 Hz, 2H), 1.80–1.71 (m, 2H), 1.45–1.20
(m, 8H), 0.88 (t, J = 7.0 Hz, 3H); 13C NMR (101 MHz,
CDCl3) d 134.1, 132.6, 129.6, 128.5, 119.6, 32.6, 31.7,
31.2, 29.2, 28.9, 25.0, 22.6, 16.3, 14.1; IR (neat) 3017,
2957, 2926, 2855, 2247, 1456, 1437, 989, 733 cmꢀ1; MS
(EI) m/z (%) 206 (M++1, 10), 205 (M+, 59), 204 (M+ꢀ1,
13), 177 (37), 176 (34), 162 (13), 148 (36), 135 (16), 134
(100), 121 (29), 120 (60), 107 (15), 106 (16), 95 (15), 94
(26), 93 (52), 91 (25), 83 (21), 82 (10), 81 (67), 80 (45), 79
(39), 77 (22), 67 (45), 55 (15). Anal. Calc. for C14H23N:
C, 81.89; H, 11.29. Found: C, 82.18; H, 11.56%.
A colorless oil, Rf 0.40 (hexane–ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3) d 8.00 (dd, J = 8.0 Hz,
2H), 7.52 (d, J = 8.2 Hz, 2H), 5.47 (dq, J = 1.3, 0.7 Hz,
1H), 5.19 (qd, J = 1.5, 1.3 Hz, 1H), 4.38 (q, J = 7.1 Hz,
2H), 2.17 (dd, J = 1.5, 0.7 Hz, 3H), 1.40 (t, J = 7.1 Hz,
3H); 13C NMR (101 MHz, CDCl3) d 166.7, 145.8, 142.7,
129.8, 129.5, 125.6, 114.7, 61.1, 21.9, 14.6; IR (neat)
2980, 2359, 2341, 1715, 1609, 1367, 1275, 1184, 1123,
1103, 1020, 899, 860, 783, 719 cmꢀ1; MS (EI) m/z (%)
190 (M+, 42), 162 (19), 146 (13), 145 (100), 115 (20);
HRMS (FAB+) Calcd for C12H14O2: M+, 190.0994.
Found: m/z 190.0993.
4.9.28. 1-(4-Ethoxycarbonylphenyl)-1-phenylethene (6pb)
A colorless solid (mp 46.7–47.3 ꢀC), Rf 0.33 (hexane–
4.9.32. (5E,7Z)-Tetradeca-5,7-dienenitrile (8bb)
1
1
ethyl acetate = 10:1). H NMR (400 MHz, CDCl3) d 8.02
A colorless oil, Rf 0.36 (hexane–ethyl acetate = 7:1). H
(d, J = 8.6 Hz, 2H), 7.41 (d, J = 8.6 Hz, 2H), 7.36–7.30
(m, 5H), 5.55 (d, J = 1.1 Hz, 1H), 5.54 (d, J = 1.1 Hz,
1H), 4.39 (q, J = 7.1 Hz, 2H), 1.41 (t, J = 7.1 Hz, 3H);
13C NMR (101 MHz, CDCl3) d 166.4, 149.3, 145.9,
140.8, 129.7, 129.5, 128.3, 128.2, 128.0, 115.8, 60.9, 14.3;
IR (KBr) 1717, 1279, 1105, 775, 702 cmꢀ1; MS (EI) m/z
(%) 253 (M++1, 18), 252 (M+, 97), 224 (14), 208 (18),
207 (100), 179 (44), 178 (68), 177 (11), 176 (11). Anal. Calc.
for C17H16O2: C, 80.93; H, 6.39. Found: C, 81.01; H,
6.47%.
NMR (400 MHz, CDCl3) d 6.37 (ddq, J = 15.1, 10.9,
1.3 Hz, 1H), 5.94 (t, J = 10.9 Hz, 1H), 5.55 (dt, J = 15.0,
7.6 Hz, 1H), 5.37 (dt, J = 10.9, 7.6 Hz, 1H), 2.35 (t,
J = 7.1 Hz, 2H), 2.27 (m, 2H), 2.16 (m, 2H), 1.77 (m,
2H), 1.41–1.21(m, 8H), 0.88 (t, J = 6.9 Hz, 3H); 13C
NMR (101 MHz, CDCl3) d 131.7, 130.8, 127.84, 127.81,
119.6, 31.7, 31.5, 29.6, 28.9, 27.7, 25.0, 22.6, 16.4, 14.1;
IR (neat) 3020, 2957, 2928, 2855, 2247, 1456, 984, 949,
735 cmꢀ1; MS (EI) m/z (%) 205 (M+, 43), 204 (M+ꢀ1,
11), 177 (51), 176 (40), 162 (14), 148 (40), 135 (15), 134
(100), 121 (30), 120 (70), 107 (16), 106 (19), 95 (16), 94
(29), 93 (50), 91 (26), 83 (31), 82 (12), 81 (79), 80 (53), 79
(44), 77 (25), 67 (53), 55 (19), 54 (10). Anal. Calc. for
C14H23N: C, 81.89; H, 11.29. Found: C, 82.19; H, 11.18%.
4.9.29. 1-(4-Methoxyphenyl)-1-phenylethene (6pg)
A colorless solid (mp 75.3–76.8 ꢀC), Rf 0.39 (hexane–
ethyl acetate = 15:1). 1H NMR (400 MHz, CDCl3) d
7.38–7.31 (m, 5H), 7.28 (d, J = 8.8 Hz, 2H), 6.87 (d,
J = 8.8 Hz, 2H), 5.41 (d, J = 1.4 Hz, 1H), 5.36 (d,
J = 1.4 Hz, 1H), 3.83 (s, 3H); 13C NMR (101 MHz, CDCl3)
d 159.6, 149.7, 142.0, 134.2, 129.6, 128.6, 128.4, 127.9,
113.7, 113.2, 55.5; IR (KBr) 3005, 2951, 2835, 1908, 1811,
1605, 1572, 1508, 1491, 1456, 1441, 1290, 1250, 1180,
1028, 901, 843, 785, 708, 581, 552 cmꢀ1; MS (EI) m/z (%)
253 (M++1, 18), 252 (M+, 97), 224 (14), 208 (18), 207
(100), 179 (44), 178 (68), 177 (11), 176 (11). Anal. Calc.
for C15H14O: C, 85.68; H, 6.71. Found: C, 85.67; H, 6.73%.
4.10. Gram-scale cross-coupling reaction of 4a with 5 b
To a mixture of K2CO3 (9.1 g, 66 mmol), (2-furyl)3P
(138 mg, 0.60 mmol), and PdCl2 (54 mg, 0.30 mmol) in
DMSO (75 mL) were added 4a (9.1 g, 33 mmol) and ethyl
4-iodobenzoate (5 b, 8.3 g, 30 mmol) sequentially, and the
resulting mixture was stirred at 35 ꢀC for 21 h. The mix-
ture was diluted with diethyl ether, washed with water
and brine, and dried over anhydrous MgSO4. Concentra-
tion in vacuo followed distillation under vacuum (1.0
mmHg) gave cyclic silyl ether 2 (3.1 g, 62%); the residue
was further purified by flash chromatography on silica
gel (hexane–ethyl acetate = 20:1 as an eluent) to give
6ab (7.6 g, 97%).
4.9.30. 1-(4-Ethoxycarbonylphenyl)-2-methylpropene (6qb)
A colorless oil, Rf 0.38 (hexane–ethyl acetate = 10:1). 1H
NMR (400 MHz, CDCl3) d 7.98 (d, J = 8.3 Hz, 2H), 7.28
(d, J = 8.3 Hz, 2H), 6.29 (s, 1H), 4.37 (q, J = 7.1 Hz,

Y. Nakao et al. / Journal of Organometallic Chemistry 692 (2007) 585–603
603
(c) S.E. Denmark, S.A. Tymonko, J. Am. Chem. Soc. 127 (2005)
8004–8005;
Acknowledgements
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This work has been supported financially by Grant-in-
Aids for Creative Scientific Research, No. 16GS0209, Sci-
entific Research on Priority Areas ‘‘Reaction Control of
Dynamic Complex’’, and COE Research on ‘‘United Ap-
proach to New Material Science’’ from MEXT.
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