Nickel(0)-catalyzed disilylative and silastannylative cyclizations of 1,3-diene and tethered aldehyde

Article abstract of DOI:10.1016/j.jorganchem.2006.03.047

Nickel(0)-catalyzed bismetallative cyclization of 1,3-diene and a tethered aldehyde in the presence of PhF₂SiSiMe₃ or Me₃SiSnBu₃ gave the corresponding cyclized product having an allylsilyl or an allylstannyl un

Full text of DOI:10.1016/j.jorganchem.2006.03.047

Journal of Organometallic Chemistry 692 (2007) 460–471
www.elsevier.com/locate/jorganchem
Nickel(0)-catalyzed disilylative and silastannylative cyclizations
of 1,3-diene and tethered aldehyde
a
b,
a,
*
Nozomi Saito , Miwako Mori *, Yoshihiro Sato
a
Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
b
Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan
Received 4 March 2006; received in revised form 20 March 2006; accepted 24 March 2006
Available online 30 August 2006
Abstract
Nickel(0)-catalyzed bismetallative cyclization of 1,3-diene and a tethered aldehyde in the presence of PhF2SiSiMe3 or Me3SiSnBu3
gave the corresponding cyclized product having an allylsilyl or an allylstannyl unit in the side chain in good yields. The cyclized product
obtained from the reaction in the presence of Me3SiSnBu3 had reactivity as an allylstannane derivative, and the coupling reaction with
benzaldehyde proceeded in a diastereoselective manner. When the silastannylative cyclization was carried out in the presence of a chiral
monodentate phosphine ligand, the cyclized product was produced as an optically active form with modest enantiomeric excess.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Nickel; Silylstannane; Disilane; Bismetallation; Bismetallative cyclization; 1,3-Diene; Aldehyde
1. Introduction
aldehyde or -ketone, bis-allene, and dienal) with a bimetal-
lic reagent (e.g., M–M0, M, M0 = B, Si, Ge, and Sn) has
been reported [2]. Recently, we have reported a nickel-cat-
alyzed stereoselective cyclization of 1,3-dienes and tethered
carbonyl groups in the presence of silane [3]. We speculated
that if a bimetallic reagent is used instead of silane in this
cyclization, a cyclized product 2 having an allylmetal unit,
which could be used for the further carbon–carbon bond-
forming reaction, would be produced (Scheme 2).
Transition metal-catalyzed addition of homo- or hetero-
bimetallic compounds to multiple bonds is of interest
because new metal–carbon bonds are formed in the prod-
uct and these bonds can be utilized in further transforma-
tions as an active bimetal functional group [1]. A
generally accepted mechanism of this reaction is shown in
Scheme 1. Oxidative addition of a bimetallic compound
to a low-valent metal complex initially occurs to produce
X–M–Y complex I. Then insertion of a multiple bond in
the substrate into the X–M or Y–M bond proceeds to give
the intermediate II or II0, and the bismetallated product III
is produced from these intermediates through reductive
elimination.
Herein, we report a nickel(0)-catalyzed bismetallative
cyclization of 1,3-diene and a tethered aldehyde in the pres-
ence of disilanes or Me3SiSnBu3 [4].
2. Results and discussion
Bismetallative cyclization between two multiple bonds
in a tether might be useful in synthetic organic chemistry,
by which cyclic compounds having an active metal–carbon
bond is produced. Indeed, the cyclization of various sub-
strates (e.g., bis-dienes, diynes, enynes, allene-yne, allene-
2.1. Bismetallative cyclization of 1,3-diene and a tethered
aldehyde in the presence of disilanes
Initially, bismetallative cyclizations of 3 in the presence
of various disilanes were investigated under optimized con-
ditions for the above-mentioned cyclization in the presence
of silane. However, the reaction did not proceed and no
desired bismetallated product was obtained (Scheme 3).
*
Corresponding authors. Tel./fax: +81 117064982.
E-mail address: biyo@pharm.hokudai.ac.jp (M. Mori).
0022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.03.047

N. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 460–471
461
would be relatively low. It is known that disilanes such as
PhCl2SiSiMe3 and PhF2SiSiMe3, in which two halogens
are attached to one silicon atom, have higher reactivity
in Pd(0)-catalyzed disilylation of enones [5] or alkynes
[6]. Thus, we investigated the bismetallative cyclizations
of 3 using these disilanes. The results of the bismetallative
cyclization of 3 using PhCl2SiSiMe3 are summarized in
Table 1.
X
R
Y
Transition Metal (M)
+
R'
R
X-Y
R'
(X, Y = Si, Sn, B, Ge...)
III
-M
Y
M
X
R
M-
R'
Y
M-
R'
X
R
R'
X-M-Y
or
R
I
II
II'
The substrate 3 was treated with 20 mol% of Ni(cod)2 and
40 mol% of PPh3 in the presence of PhCl2SiSiMe3 (1.5 equiv.)
Scheme 1.
i
and Pr2NEt (4 equiv.) in toluene at 80 °C for 12 h. Then
the reaction mixture was quenched with EtOH in the pres-
ence of Et3N for substitution of chlorides on the silicon
atom of the product for ethoxide (EtO), which was
expected to facilitate the isolation of the products. After
It is generally thought that oxidative addition of disil-
anes is the rate-determining step in bismetallation reac-
tions, and these results indicate that the reactivity of
disilanes used in the reaction toward the nickel(0) catalyst
M'
O
O
M'
O
cat. Ni(0)
M-M'
O
M
M'
or
Ni
Ni
M
M
1
2
IV
Scheme 2.
V
20 mol % Ni(cod)2
40 mol % PPh3
1.5 eq R3SiSiR'3
OSiR3
MeO2C
MeO2C
CHO
MeO2C
MeO2C
SiR'3
toluene, reflux
3
4
Me3SiSiMe3
PhMe2SiSiMe2Ph
Ph3SiSiMe3
R3SiSiR'3 =
Ph(Et2N)2SiSiMe3
Scheme 3.
Table 1
Cyclization of 3 using PhCl2SiSiMe3
20 mol % Ni(cod)
40 mol % PPh3
1.5 eq PhCl2SiSiMe3
toluene
1)
2)
2
MeO2C
CHO
OSiR3
SiR'3
OSiR3
MeO2C
+
MeO2C
MeO2C
MeO2C
SiR'3
MeO2C
EtOH, Et3N, Et2O
3
4a
4b
(1 : 1)
(SiR3, SiR'3 = SiMe3, Si(OEt)2Ph)
Run
Temp (°C)
Time (h)
Base (4 mol equiv.)
Yield (%)
1
2
3
4
80
80
80
80
12
10
17
18
iPr2NEt
Proton sponge
DABCO
38
–
–
CaCO3
–

462
N. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 460–471
the usual work-up, products 4a and 4b (ratio of 1:1) having
two silyl groups were obtained in a total yield of 38% as an
inseparable mixture (Table 1, run 1). In order to confirm
the structures of 4a and 4b, the mixture (4a:4b = 1:1) was
treated with HF/CH3CN, giving the known compounds 5
and 6 (ratio of 1:1) in total yield of 91% (Scheme 4).
It is well known that the cleavage of a Si–C bond in an
allylsilane group under acidic conditions proceeds via the
SE20 pathway [7]. This means that 5 or 6 was produced
from 4b or 4a, respectively, in a stereospecific manner,
although the regiochemistry with respect to two silyl
groups (i.e., Me3Si– and Ph(EtO)2Si–) in the products 4a
and 4b could not be determined by this transformation.
In the bismetallative cyclization of 3 using PhCl2SiSiMe3,
both the presence and the choice of bases were very signif-
icant. Thus, the reaction under similar conditions in the
absence of a base gave no desired products, and deposition
of a nickel catalyst was observed. Among the various bases
OH
SiF2Ph
NOE
1
E
2
H
H
E
(E = CO2Me)
Fig. 1. Determination of stereochemistry of 4c.
acidic conditions [7] did not proceed and the expected
product 6 was not produced, completely different from that
of the above-mentioned 4a or 4b (see, Scheme 4). Similarly,
it was found that the Si–C bond was also unreactive under
the conditions of Tamao–Fleming oxidation [8]. These
results indicate that the allylsilane unit in 4c could not be
utilized in further transformations.
2.2. Bismetallative cyclization of 1,3-diene and a tethered
aldehyde in the presence of Me3SiSnBu3
i
tested as shown in Table 1 (runs 2–4), only Pr2NEt was
effective in this reaction.
Next, the bismetallative cyclization of 3 using PhF2Si-
SiMe3 was investigated (Scheme 5). The reaction of 3 with
20 mol% of Ni(cod)2 and 40 mol% of PPh3 in the presence
of PhF2SiSiMe3 (1.5 equiv.) smoothly proceeded even at
room temperature without any base and gave the cyclized
product 4c having only one silyl group (PhF2Si–) at the
allylic position in 45% yield. It is noteworthy that the bis-
metallative cyclization of 3 using PhF2SiSiMe3 proceeded
in a completely regio- and stereoselective manner and the
product 4c was produced as the sole product, the stereo-
chemistry of which was unequivocally determined by
NOE experiments (Fig. 1).
Next, we investigated bismetallative cyclization using
Me3SiSnBu3 as a bimetallic reagent. Initially, the reaction
of 3 was examined using 20 mol% of Ni(cod)2 and
40 mol% of various phosphine ligands in the presence of
Me3SiSnBu3 (1.5 equiv.) in toluene. The results are summa-
rized in Table 2.
Although the use of PPh3, P(OEt)3, or PCy3 as a ligand
did not promote bismetallative cyclization (runs 1–3), the
reaction using PMe2Ph proceeded even at room tempera-
ture and gave the desilylated product (E)-8b instead of
the expected product (E)-8a in 23% yield as a sole product
along with the recovery of 3 in 30% yield (run 4). The ste-
reochemistry of (E)-8b was determined by NOE experi-
ments of 9, which was derived from (E)-8b by a simple
acetylation (Fig. 2).
Having obtained the product 4c as the single isomer, we
next investigated the reactivity of 4c as an allylsilane deriv-
ative (Scheme 6). The cleavage of a Si–C bond in 4c under
OSiR3
MeO2C
SiR'3
MeO2C
OH
OH
4a
MeO2C
MeO2C
MeO2C
MeO2C
HF/MeCN
+
+
OSiR3
MeO2C
6
5
91% (1 : 1)
MeO2C
SiR'3
4b
(1 : 1)
Scheme 4.
20 mol % Ni(cod)2
40 mol % PPh3
1.5 eq PhF2SiSiMe3
OH
MeO2C
MeO2C
CHO
MeO2C
MeO2C
SiF2Ph
toluene, rt, 21 hr
3
45%
4c
Scheme 5.

N. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 460–471
463
OH
MeO2C
CF3CO2H
OH
MeO2C
MeO2C
MeO2C
6
7
SiF2Ph
KF, KHCO3
H2O2
OH
MeO2C
MeO2C
4c
OH
Scheme 6.
Table 2
Effect of ligand
20 mol % Ni(cod)2
40 mol % ligand
1.5 eq Me3SiSnBu3
OSiMe3
OH
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
CHO
SnBu3
SnBu3
(E)-8a
toluene
3
(E)-8b
Run
Ligand
Temp (°C)
Time (h)
Yield (%)
1
2
3
4
a
PPh3
P(OEt)3
PCy3
Reflux
50
50
18
11
13
24
–
–
–
23a
PMe2Ph
rt
3 was recovered in 30% yied.
3'
crude product, which was obtained under the conditions
shown in Table 3, run 3, was directly treated with
CF3CO2H, a protodestannylation product 6 was obtained
in 78% yield. This result suggests that the products 8a and
8b would be produced in a yield of over 78% in the reaction
mixture and that the yield of 8a and 8b shown in Table 3,
run 3 would be somewhat decreased due to a partial decom-
position during purification and isolation.
OAc
SnBu3
1
OAc
MeO2C
MeO2C
E
H
SnBu3
2
NOE
H
E
9
(E = CO2Me)
Fig. 2. Determination of stereochemistry of 9.
Encouraged by this result, we examined the effects of a
solvent using PMe2Ph as a ligand (Table 3).
Interestingly, the bismetallative cyclization in DMF pro-
ceeded even in the absence of a phosphine ligand, and only
(E)-8a was obtained as the sole product (Scheme 7). On the
other hand, the bismetallative cyclization in a non-polar
solvent such as toluene did not proceed in the absence of
a phosphine ligand, suggesting that the coordination of a
polar solvent such as DMF would activate Me3SiSnBu3
and/or the catalyst.
The cyclization of 3 in THF provided a mixture of 8a and
8b in a ratio of 1:21 in 43% yield (Table 3, run 1). The reac-
tion in a polar solvent gave a good result (runs 2 and 3), and
the total yields of 8a and 8b reached 66% in the reaction in
DMF. In all cases shown in Table 3, the products were
obtained as isomers with respect to the olefinic geometry
in the side chain, which differed from the above-mentioned
reaction in toluene (see, Table 2, run 4). When the resulting
Next, cyclization of other substrates was examined. The
cyclization of 10 using 20 mol% of Ni(cod)2 and 40 mol%
Table 3
Nickel-catalyzed cyclization of 3 in the presence of Me3SiSnBu3
20 mol % Ni(cod)2
40 mol % PMe2Ph
1.5 eq Me3SiSnBu3
OSiMe3
OH
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
CHO
+
SnBu3
SnBu3
solvent, rt
8a
8b
3
Run
Solvent
Time (h)
Yield (%) (8a+8b)
Ratio (8a/8b)
Ratio of E/Z
8a
8b
a
1
2
3
a
THF
MECN
DMF
18
4
2
43
46
66
1/21
2.5/1
1.5/1
–
7.61
2.5/1
3.4/1
3.8/1
3.6/1
Ratio of E to Z was not determined.

464
N. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 460–471
20 mol % Ni(cod)2
1.5 eq Me3SiSnBu3
MeO2C
MeO2C
OSiMe3
CHO
MeO2C
MeO2C
SnBu3
DMF, rt, 2 hr
55%
3
(E)-8a
Scheme 7.
Table 4
Cyclization of 10 in the presence of Me3SiSnBu3
20 mol % Ni(cod)2
40 mol % ligand
1.5 eq Me3SiSnBu3
MeO2C
MeO2C
MeO2C
MeO2C
CHO
MeO2C
MeO2C
OSiMe3
OH
+
DMF, rt
10
SnBu3
SnBu3
11a
11b
Run
Ligand
Time (h)
Yield (%) (11a+11b)
Ratio (11a/11b)
1
2
PMe2Ph
–
5
6
51
31
1/7.5
1.8/1
of PMe2Ph in the presence of Me3SiSnBu3 in DMF pro-
vided the cyclohexane derivatives 11a and 11b in a ratio
of 1 to 7.5 in a total yield of 51% (Table 4, run 1).
The stereochemistry of 11a or 11b with respect to the
side chains on the cyclohexane ring was determined to be
an anti-orientation by the coupling constant between H1
and H2 protons in H1 NMR, respectively (Fig. 3).
Interestingly, the absence of a ligand in the cyclization
of 10 reversed the ratio of the products, and 11a and 11b
were produced in a ratio of 1.8:1 in 31% yield (Table 4,
run 2). It is also noteworthy that complete E-selectivity
with respect to the olefinic geometry was observed in the
reaction of the substrate 10.
13a and 13b in a ratio of 1:1.9 in 38% yield (run 1). On
the other hand, the cyclization of 12 in the absence of
PMe2Ph gave (E)-13a in 18% yield as the sole product,
the result of which is in accord with the results shown in
Scheme 7 and Table 4.
In order to confirm the structure of the cyclized prod-
ucts, 13a or 13b was converted to 15 by treatment with
CF3CO2H followed by catalytic hydrogenation with Pd/
C. The spectral data of 15 derived from 13a or 13b was
completely identical with that derived from the known
compound 16 [3e], by which the stereochemistry of 13a
or 13b with respect to the side chains on the pyrrolidine
ring was determined to be a syn-orientation (Scheme 8).
It was found that this bismetallative cyclization was
applicable to construction of a pyrrolidine ring (Table 5).
Thus, the reaction of 12 and Me3SiSnBu3 in the presence
of Ni(cod)2 and PMe2Ph afforded pyrrolidine derivatives
OH
OH
CF3CO2H
CH2Cl2
H2, Pd-C
MeOH
92%
TsN
TsN
13a or 13b
14
15
87% (from 13a)
J = 10.3 Hz
OSiMe3
J = 10.5 Hz
MeO2C
MeO2C
MeO2C
MeO2C
85% (from 13b)
H2
H2
OH
OSiEt3
1) H2, Pd-C, MeOH
2) TBAF, THF
H1
SnBu3
Fig. 3. Determination of stereochemistries of 11a and 11b.
H1
TsN
11a
11b
SnBu3
16
Scheme 8.
Table 5
Cyclization of 12 in the presence of Me3SiSnBu3
20 mol % Ni(cod)2
40 mol % ligand
1.5 eq Me3SiSnBu3
OSiMe3
OH
CHO
+
TsN
TsN
TsN
SnBu3
SnBu3
DMF, rt
12
13a
13b
Run
Ligand
Time (h)
Yield (%) (13a+13b)
Ratio (13a/13b)
Ratio of E/Z
13a
13b
1
2
PMe2Ph
–
2
2
38
18
1/1.9
>99/1
3/1
>99/1
2.4/1
–

N. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 460–471
465
Next, we tried an intermolecular nickel-catalyzed three-
component coupling reaction (Scheme 9) [3m,3n,3o,3p,9].
considered as shown in Scheme 10, path B. The nickelacy-
cle intermediate 23 is formed by oxidative cycloaddition of
1,3-diene and aldehyde in 18 to a zerovalent nickel com-
plex. Since silicon is harder than tin according to the HSAB
principle [10], the r-bond metathesis between the nickela-
cycle 23 and Me3SiSnBu3 would be expected to occur in
such a direction as shown in 24, giving the intermediate
25 [11]. Finally, the cyclized product 22 having an allylst-
annane unit would be produced via p-allylnickel intermedi-
ate 26. Both mechanisms can account for the formation
and distribution of the bismetallated products, but the real
reaction pathway cannot be determined from the present
experimental data.
When
a DMF solution of isoprene, benzaldehyde
(1 equiv.), Me3SiSnBu3 (1.5 equiv.), and Ni(cod)2 (20
mol%) in the absence of a ligand was stirred at room tem-
perature for 16 h, a coupling product 17 (E/Z = 1.3/1) was
obtained in 49% yield. It is remarkable that the regioselec-
tive C–C bond-forming reaction between isoprene and
benzaldehyde occurred to give a product 17 having an all-
ylstannane unit, although the olefinic geometry could not
be controlled.
2.3. Mechanistic consideration for bismetallative cyclization
of 1,3-diene and a tethered aldehyde in the presence of
Me3SiSnBu3
2.4. Catalytic asymmetric bismetallative cyclization in the
presence of Me3SiSnBu3
In the above-mentioned bismetallative cyclization of
various substrates in the presence of Me3SiSnBu3, products
having an allylstannane unit were always produced, and no
products having an allylsilane unit were obtained. Thus,
two plausible mechanisms consistent with these results
are considered (Scheme 10).
One mechanism starts from oxidative addition of
Me3SiSnBu3 to a zerovalent nickel catalyst (Scheme 10,
path A). A silyl(stannyl)nickel complex 19 is initially
formed by the oxidative addition. Then the insertion of
the diene unit of 18 into a Ni–Sn bond of 19 would selec-
tively occur to give p-allylnickel intermediate 20, which
reacts with the tethered aldehyde group to give 21. The
reductive elimination from 21 affords the cyclized product
22, which has an allylstannane unit, accompanying regen-
eration of a zerovalent nickel complex. Alternatively, a
mechanism involving a nickelacycle intermediate is also
We have recently reported nickel-catalyzed asymmetric
cyclization of 1,3-diene and tethered aldehyde in the pres-
ence of silane using chiral phosphorane 27 [3i,3k]. Thus,
we tried the above-mentioned bismetallative cyclization
of 3 in the presence of Me3SiSnBu3 using 27 (Scheme 11).
The reaction of 3 using Ni(cod)2 (20 mol%) and 27 [12]
(40 mol%) in the presence of Me3SiSnBu3 (1.5 equiv.) in
DMF at room temperature afforded the crude products
8a as a mixture of isomers with respect to the olefin in
the side chain. The mixture of the crude products was trea-
ted with CF3CO2H to give the corresponding protodestan-
nylation product 6 in 63% (two steps). The enantiomeric
excess and the absolute configuration of 6 were determined
to be 50% ee and (1S,2R), respectively, according to the lit-
erature [3k]. This result indicates that (1S,2R)-8a having an
allylstannane unit should be produced as an optically
active form by the bismetallative cyclization.
20 mol% Ni(cod)2
1.5 eq Me3SiSnBu3
OSiMe3
+
PhCHO
2.5. Utilization of the bismetallative cyclized product as an
allylstannane derivative
DMF, rt, 16 h
Bu3Sn
Ph
17
49% (E / Z = 1.3 / 1)
The products obtained by bismetallative cyclization in
the presence of Me3SiSnBu3 have an allylstannyl group
Scheme 9.
path A
OSiMe3
O
Ni
O Ni SiMe3
O
SiMe3
SnBu3
SnBu3
SnBu3
22
18
20
21
Me3Si-Ni-SnBu3 19
Ni(0)
Me3SiSnBu3
Ni(0)
path B
SiMe3
SiMe3
SiMe3
O
O
O
O
SnBu3
SnBu3
SnBu3
Ni
Ni
Ni
Ni
23
24
25
26
Scheme 10.

466
N. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 460–471
20 mol % Ni(cod)2
40 mol %
P Ph
OH
1
27
MeO2C
MeO2C
MeO2C
MeO2C
CHO
1.5 eq Me3SiSnBu3
CF3CO2H
2
CH2Cl2
DMF, rt, 12 hr
(1S,2R)-6: 50% ee
3
2 steps 63%
OSiMe3
1
MeO2C
MeO2C
SnBu3
2
(1S,2R)-8a
Scheme 11.
H
OH
H
MeO2C
MeO2C
BF3·OEt2
CH2Cl2
OSiMe3
MeO2C
MeO2C
+
PhCHO
SnBu3
H
H
Ph
OH
(E)-8a
28: 54%
PhCHO
SnBu3
Si
O
E
E
PhCHO
29 (E = CO2Me)
Scheme 12.
that should be useful in further transformation [13]. Thus,
the cyclized product (E)-8a was reacted with benzaldehyde
to give the coupling product 28 as the sole product in 54%
yield (Scheme 12).
The stereochemistry of 28 was tentatively assigned from
analogy to the literature on reaction of allylstannane and
aldehyde in the presence of Lewis acid [14]. It is thought that
benzaldehyde attacks allylstannane from the opposite side
with a trimethylsilyloxy group as in 29 due to steric repul-
sion, which might have controlled the stereochemistry of 28.
cyclization was carried out in the presence of a chiral
monodentate phosphine ligand, the cyclized product was
produced as an optically active form with modest enantio-
meric excess. The cyclized product obtained from the reac-
tion in the presence of Me3SiSnBu3 had reactivity as an
allylstannane derivative, and the coupling reaction with
benzaldehyde proceeded in a diastereoselective manner.
3. Experimental
3.1. General
2.6. Conclusion
All manipulations were performed under an argon
atmosphere unless otherwise mentioned. All solvents and
reagents were purified when necessary using standard pro-
cedures. Column chromatography was performed on silica
gel 60 (Merck, 70–230 mesh), and flash chromatography
was performed silica gel 60 (Merck, 230–400 mesh) using
Nickel(0)-catalyzed bismetallative cyclizations of 1,3-
diene and a tethered aldehyde in the presence of disilanes
or Me3SiSnBu3 were investigated. In the disilylative cycli-
zation, the use of PhCl2SiSiMe3 or PhF2SiSiMe3, which
has two halogens attached to one silicon atom, was effec-
tive to produce the cyclized product having an allylsilane
unit. In the silastannylative cyclization, the reaction of var-
ious substrates proceeded in DMF at room temperature in
the presence of PMe2Ph as a ligand or without any ligand
to give the corresponding cyclized product having an all-
ylstannane unit in good yield. When the silastannylative
1
the indicated solvent. H (500 MHz) and 13C (125 MHz)
spectra were recorded on a Bruker ARX-500 spectrome-
ters. 1H and 13C chemical shifts were referenced to internal
Me4Si or internal CHCl3. Mass spectra were measured on a
JEOL DX303, JEOL JMS-FAB mate, or JMS 700TZ mass
spectrometer.

N. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 460–471
467
3.2. Disilylative cyclization of 3 in the presence of
3.4. Typical procedure for bismetallative cyclization in the
PhCl2SiSiMe3 using iPr2NEt as a base (Table 1, run 1) and
confirmation of the structure of the cyclized products
(Scheme 4)
presence of Me3SiSnBu3 affording (1R*,2R*)-4,4-
bismethoxycarbonyl-2-[(E)-3-tributylstannylprop-1-
enyl]cyclopentan-1-ol ((E)-8b) (Table 2, run 4)
A solution of Ni(cod)2 (15.4 mg, 0.056 mmol) and PPh3
(29.4 mg, 0.112 mmol) in toluene (2.2 ml) was stirred at
0 °C for 20 min. To the mixture were added Pr2NEt
To a solution of Ni(cod)2 (15.4 mg, 0.056 mmol) in tol-
uene (2.2 ml) was added PMe2Ph (16 ll, 0.11 mmol), and
the mixture was stirred at 0 °C for 20 min. To the mixture
was added Me3SiSnBu3 (0.15 ml, 0.43 mmol), and the mix-
ture was stirred at the same temperature for 10 min. To the
mixture was added a solution of 3 (67.4 mg, 0.28 mmol) in
toluene (3.4 ml), and the mixture was stirred at room tem-
perature for 24 h. After removal of the solvent, the residue
was purified by flash column chromatography on silica gel
(hexane/Et2O, 10:1) to give (E)-8b (35.1 mg, 23%) as a col-
orless oil along with 3 (20.0 mg, 30%). IR (neat) 3854, 1736,
i
(0.2 ml, 1.15 mmol) and PhCl2SiSiMe3 (98 ll, 0422 mmol),
and the mixture was stirred at 0 °C for 10 min. To the
mixture was added a solution of 3 [3k] (67.4 mg,
0.28 mmol) in toluene (3.4 ml), and the mixture was stir-
red at 80 °C for 12 h. To the mixture were added Et2O
(2.8 ml), Et3N (0.14 ml, 1.00 mmol), and EtOH (74 ml,
1.26 mmol) at 0 °C, and the mixture was stirred at the
same temperature for 1.5 h. The mixture was filtered
through a pad of CeliteÒ, and the filtrate was concen-
trated. The residue was purified by flash column chroma-
tography on silica gel (hexane/AcOEt, 10:1) to give 4a
and 4b (50.3 mg, 38%) as an inseparable mixture. To
the mixture of 4a and 4b (13.0 mg, 25.5 mmol) in CH3CN
(1 ml) was added HF–CH3CN solution (9:1, 1 ml) at 0 °C,
and the mixture was stirred at room temperature for 1 h.
To the mixture was added satd. NaHCO3 aqueous solu-
tion, and the mixture was extracted with Et2O. The com-
bined organic layer was washed with brine, dried over
Na2SO4. After removal of the solvent, the residue was
purified by column chromatography on silica gel (hex-
ane/AcOEt, 3:1–2:1) to give 5 and 6 (5.6 mg, 91%, ratio
of 1:1) as an inseparable mixture, whose spectral data
were completely identical with those previously reported
[3k].
1654, 1264, 1170 cmꢀ1 1H NMR (500 MHz, CDCl3) d
;
0.80–0.92 (m, 15H), 1.25–1.33 (m, 6H), 1.38–1.55 (m,
6H), 1.73 (d, J = 3.5 Hz, 1H), 1.75 (ddd, J = 8.6 Hz,
2
2J(119Sn–H) = 29.4 Hz, J(117Sn–H) = 29.4 Hz, 2H), 2.29–
2.39 (m, 2H), 2.40–2.48 (m, 2H), 2.60 (m, 1H), 3.71 (s,
3H), 3.74 (s, 3H), 4.09 (m, 1H), 5.25 (dd, J = 15.3,
7.3 Hz, 1H), 5.73 (dt, J = 15.3, 8.6 Hz, 1H); 13C NMR
(67.4 MHz, CDCl3) d 9.20, 13.5, 14.8, 27.3, 29.1 36.9,
42.3, 48.5, 52.8, 52.9, 58.4, 75.2, 221.4, 133.5, 173.1,
163.2; EI-LRMS m/z 532 (M+), 475, 369, 291, 235, 177,
164, 105; EI-HRMS calcd for C24H44O5120Sn 532.2210,
found 532.2187.
3.5. (1R*,2R*)-1-Acetoxy-4,4-bismethoxycarbonyl-2-[(E)-
3-tributylstannylprop-1-enyl]cyclopentane (9)
To a solution of (E)-8b (24.0 mg, 45 mmol) in pyridine
(0.1 ml) was added Ac2O (0.1 ml), and the mixture was stir-
red at room temperature for 11 h. After removal of the sol-
vent, the residue was purified by flash column
chromatography on silica gel (hexane/Et2O, 8:1, containing
1% Et3N) to give 9 (23.3 mg, 90%) as a colorless oil. IR
3.3. (1R*,2R*)-2-[(E)-3-Difruorophenylsilylprop-1-enyl]-
4,4-dimethoxycarbonyl-cyclopentan-1-ol (4c) (disilylative
cyclization of 3 in the presence of PhF2 SiSiMe3 shown in
Scheme 5)
1
A solution of Ni(cod)2 (15.4 mg, 0.056 mmol) and PPh3
(29.4 mg, 0.112 mmol) in toluene (2.2 ml) was stirred at
0 °C for 20 min. To the mixture was added PhF2SiSiMe3
(90 ll, 042 mmol), and the mixture was stirred for
10 min. To the mixture was added a solution of 3
(67.4 mg, 0.28 mmol) in toluene (3.4 ml), and the mixture
was stirred at room temperature for 12 h. After removal
of the solvent, the residue was purified by flash column
chromatography on silica gel (hexane/AcOEt, 3:1–2:1) to
give 4c (48.1 mg, 45%) as a colorless oil. IR (neat) 3536,
1732, 1654, 1602, 1264 cmꢀ1; 1H NMR (500 MHz, CDCl3)
d 1.95 (br d, J = 3.4 Hz, 1H), 2.45 (dd, J = 13.6, 11.9 Hz,
1H), 2.48–2.54 (m, 2H), 2.57 (br d, J = 14.5 Hz, 1H),
2.74 (m, 1H), 3.46 (d, J = 6.8 Hz, 2H), 3.80 (s, 3H), 3.83
(s, 3H), 4.26 (br s, 1H), 5.76 (dd, J = 15.6, 7.0 Hz, 1H),
5.83 (dt, J = 15.6, 6.8 Hz, 1H), 7.23–7.30 (m, 3H), 7.34–
7.39 (m, 2H); EI-LRMS m/z 241 (M+ꢀSiF2Ph), 181, 174,
145, 113, 77, 59; EI-HRMS calcd for C12H17O5 241.1138
(M+ꢀSiF2Ph), found 241.1159.
(neat) 1742, 1738, 1654, 1232 cmꢀ1; H NMR (500 MHz,
CDCl3) d 0.77–0.91 (m, 15H), 1.25-1.33 (m, 6H), 1.38–
1.55 (m, 6H), 1.70 (ddd, J = 8.6 Hz, 2J(119Sn–
H) = 29.5 Hz, 2J(117Sn–H) = 29.5 Hz, 2H), 2.00 (s, 3H),
2.31 (dd, J = 13.4, 12.2 Hz, 1 H), 2.38 (dd, J = 13.4,
7.5 Hz, 1H), 2.29–2.56 (m, 2H), 2.69 (m, 1H), 3.71 (s,
3H), 3.73 (s, 3H), 5.06 (m, 1H), 5.15 (dd, J = 15.1,
8.0 Hz, 1H), 5.77 (dt, J = 15.1, 8.6 Hz, 1H); EI-LRMS
m/z 574 (M+), 517, 291, 235, 179, 164, 105; EI-HRMS
calcd for C26H46O6120Sn 574.2316, found 574.2305.
3.6. (1R*,2R*)-4,4-Bismethoxycarbonyl-2-(3-tributyl-
stannylprop-1-enyl)-1-trimethylsilyloxycyclopentane (8a)
and (1R*,2R*)-4,4-bismethoxycarbonyl-2-(3-tributyl-
stannylprop-1-enyl)cyclopentan-1-ol (8b) (Table 3, run 3)
Following the above-mentioned typical procedure for
bismetallative cyclization in the presence of Me3SiSnBu3,
a crude product, which was obtained from 3 (67.4 mg,

468
N. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 460–471
0.28 mmol), Ni(cod)2 (15.4 mg, 0.056 mmol), PMe2Ph
(16 ll, 0.11 mmol), and Me3SiSnBu3 (0.15 ml, 0.43 mmol)
in DMF (5.6 ml) at room temperature for 2 h, was purified
by flash column chromatography on silica gel (hexane/
Et2O, 100:1–10:1, containing 1% Et3N) to give an insepara-
ble mixture of (E)-8a and (Z)-8a (67.6 mg, 40%, E:Z=3.6:1)
along with (E)-8b (29.2 mg, 20%) and (Z)-8b (8.7 mg, 6%)
as a colorless oil.
173.8; EI-LRMS m/z 604 (M+), 547, 483, 291, 235, 177,
164, 105; EI-HRMS calcd for C27H52O5Si120Sn 604.2606,
found 604.2628.
3.8. Bismetallative cyclization of 10 in the presence of
Me3SiSnBu3 affording (1R*,2S*)-4,4-bismethoxycarbonyl-
2-[(E)-3-tributylstannylprop-1-enyl]-2-trimethyl-
silyloxycyclohexane (11a) and (1R*,2S*)-4,4-bismeth-
oxycarbonyl-2-[(E)-3-tributylstannnylprop-1-
Compound (E)-8a: 1H NMR (500 MHz, CDCl3) d 0.057
(s, 9H), 0.82–0.91 (m, 15H), 1.26–1.34 (m, 6H), 1.40–1.56
(m, 6H), 1.70 (ddd, J = 8.5 Hz, 2J(119Sn–H) = 29.6 Hz,
2J(117Sn–H) = 29.6 Hz, 2H), 2.15 (dd, J = 12.3, 6.7 Hz,
1H), 2.34 (dd, J = 14.1, 3.8 Hz, 1H), 2.39 (dd, J = 14.1,
1.4 Hz, 1H), 2.42 (m, 1H), 2.46 (m, 1H), 3.70 (s, 3H),
3.72 (s, 3H), 4.05 (m, 1H), 5.23 (dd, J = 15.2, 7.9 Hz,
1H), 5.73 (dt, J = 15.2, 8.5 Hz, 1H).
enyl]cyclohexan-1-ol (11b) (Table 4, run 1)
Following the above-mentioned typical procedure for
bismetallative cyclization in the presence of Me3SiSnBu3,
a crude product, which was obtained from 10 (69.5 mg,
0.27 mmol), Ni(cod)2 (15.2 mg, 0.055 mmol), PMe2Ph
(16 ll, 0.112 mmol), and Me3SiSnBu3 (0.145 ml, 0.42
mmol) in DMF (5.5 ml) at room temperature for 5 h, was
purified by flash column chromatography on silica gel (hex-
ane/Et2O, 100:1–10:1, containing 1% Et3N) to give 11a
(10.6 mg, 6%) and 11b (67.0 mg, 45%) as a colorless oil,
respectively.
Compound (Z)-8a: 1H NMR (500 MHz, CDCl3) d 0.051
(s, 9H), 0.82–0.91 (m, 15H), 1.26–1.34 (m, 6H), 1.40–1.56
(m, 6H), 1.60–1.80 (m, 2H), 2.23 (dd, J = 13.4, 7.9 Hz,
1H), 2.32–2.51 (m, 3H), 2.77 (m, 1H), 3.70 (s, 3H), 3.72
(s, 3H), 4.08 (m, 1H), 5.12 (dd, J = 10.0, 10.0 Hz, 1H),
5.57 (m, 1H).
Spectral data of 11a: IR (neat) 1738, 1654, 1206,
1
Compound (Z)-8b: IR (neat) 3828, 1736, 1654,
1108 cmꢀ1; H NMR (500 MHz, CDCl3) d 0.081 (s, 9H),
1
1264 cmꢀ1; H NMR (500 MHz, CDCl3) d 0.84–0.91 (m,
0.78–0.91 (m, 6H), 0.89 (t, J = 7.3 Hz, 9H), 1.25–1.35 (m,
6H), 1.38–1.53 (m, 6H), 1.63–1.60 (m, 2H), 1.60–1.89 (m,
3H), 1.91 (br d, J = 13.3 Hz, 1H), 2.03 (m, 1H), 2.32–
2.38 (m, 2H), 3.23 (ddd, J = 10.3, 10.3, 4.4 Hz, 1H), 3.68
(s, 3H), 3.73 (s, 3H), 5.08 (dd, J = 15.7, 7.4 Hz, 1H), 5.57
(dd, J = 15.7, 8.0 Hz, 1H); 13C NMR (125 MHz, CDCl3)
d 0.42, 9.2, 13.7, 14.4, 27.5, 29.2, 30.0, 32.3, 36.4, 44.9,
52.4, 52.6, 54.7, 74.3, 127.2, 130.1; EI-LRMS m/z 618
(M+), 547, 561, 327, 291, 178, 119; EI-HRMS calcd for
C28H54O5Si120Sn 618.2762, found 618.2791.
15H), 1.25–1.34 (m, 6H), 1.40–1.54 (m, 6H), 1.74 (ddd,
J = 9.2 Hz, 2J(119Sn–H) = 30.4 Hz, 2J(117Sn–H) = 30.4
Hz, 2H), 1.80 (br d, J = 3.3 Hz, 1H), 2.28 (dd, J = 13.6,
11.3 Hz, 1H), 2.43 (dd, J = 13.6, 8.1 Hz, 1H), 2.45–2.50
(m, 2 H), 2.86 (m, 1H), 3.74 (s, 3H), 3.75 (s, 3H), 4.19
(m, 1H), 5.07 (dd, J = 9.7, 9.7 Hz, 1H), 5.76 (dt, J = 9.7,
9.2 Hz, 1H); EI-LRMS m/z 532 (M+), 475, 291, 233, 177,
164, 105; EI-HRMS calcd for C24H44O5120Sn 532.2210,
found 532.2186.
Spectral data of 11b: IR (neat) 3566, 1736, 1654, 1206,
1
3.7. Bismetallative cyclization of 3 in the presence of
Me3SiSnBu3 without ligands (Scheme 7)
1104 cmꢀ1; H NMR (500 MHz, CDCl3) d 0.81–0.95 (m,
6H), 0.89 (t, J = 7.1 Hz, 9H), 1.25–1.36 (m, 6H), 1.40–
1.61 (m, 8H), 1.65–1.83 (m, 3H), 1.94 (br s, 1H), 1.90–
2.13 (m, 2H), 2.34 (br d, J = 13.5 Hz, 1H), 2.41 (br d,
J = 3.5 Hz, 1H), 3.19 (ddd, J = 10.5, 10.5, 4.0 Hz, 1H),
3.69 (s, 3H), 3.75 (s, 3H), 4.97 (dd, J = 15.2, 9.0 Hz, 1H),
5.78 (dt, J = 15.2, 8.5 Hz, 1H); EI-LRMS m/z 546 (M+),
489, 369, 291, 255, 238, 233, 177, 119; EI-HRMS calcd
for C25H46O5120Sn 546.2367, found 546.2387.
Following the above-mentioned typical procedure for
bismetallative cyclization in the presence of Me3SiSnBu3,
a crude product, which was obtained from 3 (67.4 mg,
0.28 mmol), Ni(cod)2 (15.4 mg, 0.056 mmol), and Me3SiS-
nBu3 (0.15 ml, 0.43 mmol) in DMF (5.6 ml) at room tem-
perature for 2 h, was purified by flash column
chromatography on silica gel (hexane/Et2O, 100:1–10:1,
containing 1% Et3N) to give (E)-8a (93.2 mg, 55%) as a col-
orless oil.
3.9. Bismetallative cyclization of 12 in the presence of
Me3SiSnBu3 (Table 5, run 1)
Spectral data of pure (E)-8a: IR (neat) 1738, 1654,
1
1250 cmꢀ1; H NMR (500 MHz, CDCl3) d 0.057 (s, 9H),
Following the above-mentioned typical procedure for
bismetallative cyclization in the presence of Me3SiSnBu3,
a crude product, which was obtained from 12 (78.2 mg,
0.28 mmol), Ni(cod)2 (15.4 mg, 0.056 mmol), PMe2Ph
(16 ll, 0.11 mmol), and Me3SiSnBu3 (0.15 ml, 0.43 mmol)
in DMF (5.6 ml) at room temperature for 2 h, was purified
by flash column chromatography on silica gel (hexane/
Et2O, 100:1–1:1, containing 1% Et3N) to give an insepara-
ble mixture of (E)- and (Z)-13a (27.6 mg, 6%) and an insep-
arable mixture of (E)- and (Z)-13b (40.0 mg, 13%).
0.82–0.91 (m, 15H), 1.26–1.34 (m, 6H), 1.40–1.56 (m,
6H), 1.70 (ddd, J = 8.5 Hz, 2J(119Sn–H) = 29.6 Hz,
2J(117Sn–H) = 29.6 Hz, 2H), 2.15 (dd, J = 12.3, 6.7 Hz,
1H), 2.34 (dd, J = 14.1, 3.8 Hz, 1H), 2.39 (dd, J = 14.1,
1.4 Hz, 1H), 2.42 (m, 1H), 2.46 (m, 1H), 3.70 (s, 3H),
3.72 (s, 3H), 4.05 (m, 1H), 5.23 (dd, J = 15.2, 7.9 Hz,
1H), 5.73 (dt, J = 15.2, 8.5 Hz, 1H); 13C NMR
(125 MHz, CDCl3) d 0.01, 9.14, 13.7, 14.4, 27.3, 29.2,
38.2, 43.8, 49.2, 52.5, 52.7, 58.5, 76.1, 124.0, 130.7, 172.5,

N. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 460–471
469
1H NMR peaks assignable to those of (E)-13a: 1H NMR
(500 MHz, CDCl3) d ꢀ0.063 (s, 9H), 0.76–0.91 (m, 6H),
0.89 (t, J = 7.2 Hz, 9H), 1.24–1.33 (m, 6H), 1.36–1.54 (m,
6H), 1.58–1.73 (m, 2H), 2.42 (s, 3H), 2.53 (m, 1H), 3.03
(dd, J = 10.8, 9.0 Hz, 1H), 3.18 (br d, J = 11.1 Hz, 1H),
3.40 (dd, J = 10.8, 8.3 Hz, 1H), 3.45 (dd, J = 11.3,
3.6 Hz, 1H), 3.99 (m, 1H), 5.02 (dd, J = 15.3, 8.4 Hz,
1H), 5.60 (dt, J = 15.3, 8.5 Hz, 1H), 7.29 (d, J = 8.1 Hz,
2H), 7.71 (d, J = 8.1 Hz, 2H).
3.03 (dd, J = 10.8, 9.0 Hz, 1H), 3.18 (br d, J = 11.1 Hz,
1H), 3.40 (dd, J = 10.8, 8.3 Hz, 1H), 3.45 (dd, J = 11.3,
3.6 Hz, 1H), 3.99 (m, 1H), 5.02 (dd, J = 15.3, 8.4 Hz,
1H). 5.60 (dt, J = 15.3, 8.5 Hz, 1H), 7.29 (d,
J = 8.1 Hz, 2H), 7.71 (d, J = 8.1 Hz, 2H); 13C NMR
(125 MHz, CDCl3) d ꢀ0.22, 9.18, 13.7, 14.6, 27.3, 29.0,
48.1, 51.0, 57.0, 74.6, 119.7, 126.5, 127.6, 129.5, 133.3,
143.0; EI-LRMS m/z 643 (M+), 586, 291, 235, 209,
177, 108; EI-HRMS calcd for C29H53NO3SSi120 Sn
643.2537, found 643.2542.
1H NMR peaks assignable to those of (Z)-13a: 1H
NMR (500 MHz, CDCl3) d ꢀ0.063 (s, 9H), 0.76–0.91 (m,
6H), 0.89 (t, J = 7.2 Hz, 9H), 1.24–1.33 (m, 6H), 1.36–
1.54 (m, 6H), 1.58–1.73 (m, 2H), 2.44 (s, 3H), 2.95 (m,
1H), 3.03 (dd, J = 11.0, 1.6 Hz, 1H), 3.50–3.55 (m, 3H),
4.20 (m, 1H), 4.80 (dd, J = 9.7, 9.5 Hz, 1H), 5.81 (dt,
J = 9.7, 9.6 Hz, 1H), 7.29 (d, J = 8.1 Hz, 2H), 7.71 (d,
J = 8.1 Hz, 2H).
3.11. Confirmation of the structure of the cyclized products
13a and 13b (Scheme 8)
3.11.1. Conversion of 13a to (3S*,4S*)-3-hydroxy-4-(prop-
2-enyl)-1-(p-toluenesulfonyl)pyrrolidine (14)
1H NMR peaks assignable to those of (E)-13b: 1H NMR
(500 MHz, CDCl3) d 0.80–0.92 (m, 6H), 0.89 (t, J =7.3 Hz,
9H), 1.23–1.33 (m, 6H), 1.35–1.52 (m, 6H), 1.60 (br s, 1H),
1.72 (ddd, J = 8.6 Hz, 2J(119Sn–H) = 29.4, 2J(117Sn–
H) = 29.4 Hz, 2H), 2.43 (s, 3H), 2.67 (m, 1H), 3.10 (dd,
J = 9.9, 9.9 Hz, 1H), 3.31 (br d, J = 11.2 Hz, 1H), 3.46
(dd, J = 9.9, 7.8 Hz, 1H), 3.51 (dd, J = 11.2, 4.3 Hz, 1H),
4.09 (m, 1H), 5.06 (dd, J = 15.4, 7.6 Hz, 1H), 5.71 (dt,
J = 15.4, 8.6 Hz, 1H), 7.32 (d, J = 8.1 Hz, 2H), 7.73 (d,
J = 8.1 Hz, 2H).
To a solution of 13a (29.7 mg, 0.046 mmol) in CH2Cl2
(2 ml) was added CF3CO2H (37 ll, 0.048 mmol) at 0 °C,
and the mixture was stirred at room temperature for
10 min. After removal of the solvent, the residue was puri-
fied by flash column chromatography on silica gel (hexane/
AcOEt, 3:2) to give 14 (11.3 mg, 87%) as a colorless oil. IR
(neat) 3510, 1654, 1598, 1338, 1160 cmꢀ1 1H NMR
;
(500 MHz, CDCl3) d 1.46 (br d, J = 4.5 Hz, 1H), 2.03–
2.15 (m, 2H), 2.23 (ddd, J = 14.0, 6.6, 6.6 Hz, 1H), 2.43
(s, 3H), 2.98 (dd, J = 10.0, 10.0 Hz, 1H), 3.36 (br d,
J = 11.3 Hz, 1H), 1.90 (dd, J = 11.3, 4.2 Hz, 1H), 3.48
(dd, J = 10.0, 7.5 Hz, 1H), 4.20 (m, 1H), 5.01 (d,
J = 10.1 Hz, 1H), 5.05 (d, J = 17.0 Hz, 1H), 5.73 (dddd,
J = 17.3, 10.1, 6.6, 6.6 Hz, 1H), 7.32 (d, J = 8.2 Hz, 2H),
7.72 (d, J = 8.2 Hz, 2H); EI-LRMS m/z 281 (M+), 264,
239, 184, 155, 126, 108, 91, 68; EI-HRMS calcd for
C14H19NO3S 281.1085, found 281.1075.
1H NMR peaks assignable to those of (Z)-13b: 1H
NMR (500 MHz, CDCl3) d 0.80–0.92 (m, 6H), 0.89 (t, J
=7.3 Hz, 9H), 1.23–1.33 (m, 6H), 1.35–1.52 (m, 6H), 1.60
2
(br s, 1H), 1.69 (ddd, J = 9.6 Hz, J(119Sn–H) = 30.0 Hz,
2J(117Sn–H) = 30.0 Hz, 2H), 2.43 (s, 3H), 2.92 (m, 1H),
3.04 (dd, J = 11.2, 1.6 Hz, 1H), 3.30 (dd, J = 11.3,
1.6 Hz, 1H), 3.51 (m, 1H), 3.56 (dd, J = 11.2, 4.6 Hz,
1H), 4.18 (m, 1H), 4.87 (dd, J = 9.7, 9.7 Hz, 1H), 5.81
(dt, J = 9.7, 9.6 Hz, 1H), 7.32 (d, J = 8.1 Hz, 2H), 7.73
(d, J = 8.1 Hz, 2H).
3.11.2. Conversion of 13b to 14
According to the similar procedure for conversion of
13a to 14, a crude product, which was obtained from
13b (20.1 mg, 0.031 mmol) and CF3CO2H (28 ll,
0.036 mmol) in CH2Cl2 (2 ml) at room temperature for
10 min, was purified by flash column chromatography
on silica gel (hexane/AcOEt, 3:2) to give 14 (8.4 mg,
85%) as a colorless oil, whose spectral data was com-
pletely identical with the above-mentioned compound 14
obtained from 13a.
3.10. Bismetallative cyclization of 12 in the presence of
Me3SiSnBu3without ligands (Table 5, run 2) affording
(3S*,4S*)-4-[(E)-3-tributylstannylprop-1-enyl]-2-tri-
methylsilyloxy-1-(p-toluenesulfonyl)pyrrolidine ((E)-13a)
Following the above-mentioned typical procedure for
bismetallative cyclization in the presence of Me3SiSnBu3,
a crude product, which was obtained from 12 (78.2 mg,
0.28 mmol), Ni(cod)2 (15.4 mg, 0.056 mmol), and Me3SiS-
nBu3 (0.15 ml, 0.43 mmol) in DMF (5.6 ml) at room tem-
perature for 2 h, was purified by flash column
chromatography on silica gel (hexane/Et2O, 100:1–1:1,
containing 1% Et3N) to give an inseparable mixture of
(E)-13a (32.0 mg, 18%) as a colorless oil. IR (neat)
3.11.3. Conversion of 14 to 15
A solution of 14 (8.4 mg, 0.030 mmol) and 10% Pd–C
(1.6 mg, 1.5 lmol) in CH3OH (1 ml) was stirred at room
temperature for 12 h under an atmosphere of hydrogen.
The reaction mixture was filtered through a pad of silica
gel, and the filtrate was concentrated. The residue was puri-
fied by column chromatography on silica gel (Et2O) to give
15 (7.8 mg, 98%) as a colorless oil, whose spectral data was
identical with those previously reported [3e].
1654, 1598, 1348, 1164, 1020 cmꢀ1
;
1H NMR
(500 MHz, CDCl3) d ꢀ0.063 (s, 9H), 0.76–0.91 (m, 6H),
0.89 (t, J = 7.2 Hz, 9H), 1.24–1.33 (m, 6H), 1.36–1.54
(m, 6H), 1.58–1.73 (m, 2H), 2.42 (s, 3H), 2.53 (m, 1H),

470
N. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 460–471
3.12. Intermolecular bismetallative coupling of isoprene and
benzaldehyde (Scheme 9)
configuration of 6 was determined according to the method
previously reported [3k].
To a solution of Ni(cod)2 (16.5 mg, 0.06 mmol) in DMF
were added isoprene (30 ll, 0.3 mmol) and benzaldehyde
(30 ll, 0.3 mmol) at 0 °C, and the mixture was stirred at
room temperature for 16 h. After removal of the solvent,
the residue was purified by flash column chromatography
on silica gel (hexane, containing 1% Et3N) to give (E)-17
(43.7 mg, 28%) and (Z)-17 (33.7 mg, 21%) as a colorless
oil, respectively.
3.14. Reaction of the cyclized product (E)-8a with
benzaldehyde (Scheme 12)
To a solution of (E)-8a (77.9 mg, 0.129 mmol) in CH2Cl2
(1.5 ml) were added benzaldehyde (15.7 mg, 0.148 mmol)
and BF3 Æ OEt2 (57 ll, 0.450 mmol) at ꢀ78 °C, and the mix-
ture was stirred at the same temperature for 1.5 h. The reac-
tion temperature was slowly raised to 0 °C, and the mixture
was stirred at 0 °C for 1.5 h. To the mixture was added satd.
NaHCO3 aqueous solution, and the solution was extracted
with AcOEt. The organic layer was washed with brine, and
dried over Na2SO4. After removal of the solvent, the residue
was dissolved in THF (2 ml), and CsF (98.0 mg,
0.645 mmol) was added to the solution. The mixture was
stirred at room temperature for 2 h. After removal of the
solvent, the residue was purified by column chromatogra-
phy on silica gel (hexane/AcOEt, 2:1) to give 28 (24.5 mg,
54%) as a colorless oil. IR (neat) 3418, 1732, 1654, 1604,
Compound (E)-17: IR (neat) 1654, 1602, 1072 cmꢀ1
;
1H NMR (500 MHz, CDCl3) d 0.01 (s, 9H), 0.72–0.85
(m, 6H), 0.89 (t, J = 7.3 Hz, 9H), 1.25–1.33 (m, 6H),
1.40–1.45 (m, 6H), 1.55 (s, 3H), 1.51–1.70 (m, 2H), 2.29
(dd, J = 13.5, 6.0 Hz, 1H), 2.41 (dd, J = 13.5, 7.2 Hz,
1H), 4.69 (dd, J = 7.2, 6.0 Hz, 1H), 5.28 (t, J = 9.0 Hz,
1H), 7.18–7.32 (m, 5H); 13C NMR (125 MHz, CDCl3) d
0.12, 9.3, 10.7, 13.7, 16.4, 27.4, 29.2, 51.1, 74.8, 125.7,
126.1, 126.3, 126.8, 127.9, 145.5; EI-LRMS m/z 470,
323, 291, 267, 235, 209, 179, 158; EI-HRMS calcd for
C27H50OSi120Sn 538.2653, found 538.2669.
1
1202, 1168 cmꢀ1; H NMR (500 MHz, CDCl3) d 1.97 (m,
Compound (Z)-17: IR (neat) 1654, 1602, 1082 cmꢀ1; 1H
NMR (500 MHz, CDCl3) d 0.03 (s, 9H), 0.75–0.91 (m, 6H),
0.88 (t, J = 7.3 Hz, 9H), 1.24–1.32 (m, 6H), 1.38–1.50 (m,
6H), 1.50–1.68 (m, 2H), 1.61 (s, 3H), 2.26 (dd, J = 13.3,
5.9 Hz, 1H), 2.43 (dd, J = 13.3, 5.9 Hz, 1H), 4.74 (dd,
J = 13.3, 7.5 Hz, 1H), 5.35 (t, J = 9.2 Hz, 1H), 7.20–7.34
(m, 5H); 13C NMR (125 MHz, CDCl3) d 0.09, 9.4, 10.6,
13.7, 24.4, 27.4, 29.2, 43.3, 74.1, 125.8, 125.9, 126.3,
126.8, 127.9, 145.6; EI-LRMS m/z 470, 323, 291, 267,
235, 209, 179, 158; EI-HRMS calcd for C27H50OSi120Sn
538.2653, found 538.2648.
1H), 2.20 (dd, J = 13.8, 12.1 Hz, 1H), 2.29 (dd, J = 13.8,
7.8 Hz, 1H), 2.46–2.56 (m, 2H), 2.58 (br s, 1H), 2.65 (ddd,
J = 9.7, 9.7, 8.3 Hz, 1H), 3.16 (br s, 1H), 3.70 (s, 3H),
3.74 (s, 3H), 4.54 (br s, 1H), 4.67 (br d, J = 8.3 Hz, 1H),
4.81 (d, J = 9.7 Hz, 1H), 4.82 (d, J = 17.7, Hz, 1H), 5.32
(ddd, J = 17.7, 9.7, 9.7 Hz, 1H), 7.23–7.27 (m, 3H), 7.28–
7.33 (m, 2H); 13C NMR (125 MHz, CDCl3) d 38.0, 42.7,
48.8, 51.6, 52.8, 52.9, 57.6, 73.2, 77.8, 117.3, 127.0, 127.9,
128.3, 173.2, 173.3; EI-LRMS m/z 330 (M+ꢀH2O), 242,
224, 210, 192, 164, 105, 77, 59; EI-HRMS calcd for
C19H22O5 (M+ꢀH2O) 330.1467, found 330.1476.
3.13. Asymmetric bismetallative cyclization of 3 in the
presence of Me3SiSnBu3 using 27 as a chiral ligand (Scheme
11)
Acknowledgement
This work was financially supported by Grant-in-Aid
for Scientific Research on Priority Areas (Nos. 15036204
and 16033203, ‘‘Reaction Control of Dynamic Com-
plexes’’) from the Ministry of Education, Culture, Sports,
Science and Technology, Japan. N.S. acknowledges JSPS
Research Fellowships for Young Scientists for support.
To a solution of Ni(cod)2 (15.4 mg, 0.056 mmol) in
DMF (0.8 ml) was added a solution of 27 (21.5 mg,
0.112 mmol) in DMF (1.4 ml) at 0 °C, and the mixture
was stirred at the same temperature for 20 min. To the
solution were added Me3SiSnBu3 (0.15 ml, 0.43 mmol)
and a solution of 3 (67.4 mg, 0.28 mmol) in DMF
(3.4 ml), and the mixture was stirred at room temperature
for 12 h. After removal of the solvent, the residue was dis-
solved in CH2Cl2 (2.8 ml), and to the mixture was added
CF3COOH (0.11 ml, 1.43 mmol). The mixture was stirred
at room temperature for 10 min. After removal of the sol-
vent, the residue was dissolved in THF (2.8 ml), and CsF
(213 mg, 1.4 mmol) was added to the mixture. Then the
mixture was stirred at room temperature for 2 h. After
removal of the solvent, the residue was purified by flash
column chromatography on silica gel (hexane/AcOEt,
3:1) to give (1S,2R)-6 (42.7 mg, two steps 63%) as a color-
less oil, whose spectral data was identical with those previ-
ously reported [3k]. The enantiomeric excess and absolute
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