Palladium-catalyzed carbostannylation by means of reagents containing carbon-tin-halogen inter-element linkages

Article abstract of DOI:10.1016/S0022-328X(00)00483-6

Reagents containing carbon-tin-halogen inter-element linkages were effective for palladium-catalyzed carbostannylation. In situ generated allyltin trichlorides add to carbon-carbon double bonds of bicyclo[2.2.1]hept-2-ene (norbornene) and bicyclo[2.2.1]hepta-2,5-diene (norbornadiene), stereoselectively, under the catalysis of palladium(0) species in good yields. The regioselectivity of unsymmetrically substituted allylic reagents dramatically alters with the choice of the tin(II) salt. Aryltin trichlorides undergo palladium-catalyzed arylstannylation of norbornene, giving a mixture of products composed of that taking one norbornene and that taking two norbornenes. The product ratio is dependent on the choice of the solvent and electronic nature of the aromatic substituent.

Full text of DOI:10.1016/S0022-328X(00)00483-6

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 611 (2000) 433–444
Palladium-catalyzed carbostannylation by means of reagents
containing carbon–tin–halogen inter-element linkages
a
a
a
a
Keigo Fugami , Kentaro Kawata , Tatsuki Enokido , Yukie Mishiba ,
a
a
b
Sachiko Hagiwara , Yasuyuki Hirunuma , Daisuke Koyama ,
b
a,
Masayuki Kameyama , Masanori Kosugi *
a
Department of Chemistry, Faculty of Engineering, Gunma Uni6ersity, Kiryu, Gunma 376-8515, Japan
b
Oyama National College of Technology, Oyama, Tochigi, 323-0806, Japan
Received 1 March 2000; received in revised form 17 April 2000; accepted 18 April 2000
Abstract
Reagents containing carbon–tin–halogen inter-element linkages were effective for palladium-catalyzed carbostannylation. In
situ generated allyltin trichlorides add to carbon–carbon double bonds of bicyclo[2.2.1]hept-2-ene (norbornene) and bicy-
clo[2.2.1]hepta-2,5-diene (norbornadiene), stereoselectively, under the catalysis of palladium(0) species in good yields. The
regioselectivity of unsymmetrically substituted allylic reagents dramatically alters with the choice of the tin(II) salt. Aryltin
trichlorides undergo palladium-catalyzed arylstannylation of norbornene, giving a mixture of products composed of that taking
one norbornene and that taking two norbornenes. The product ratio is dependent on the choice of the solvent and electronic
nature of the aromatic substituent. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Palladium and compounds; Allylation; Arylation; Alkenes; Tin and compounds
possess a p-accepting substituent [6]. Yamaguchi et al.
have widened the scope of the reaction by developing
stanna-oxa-ene-type reactions via in situ generation of
nucleophilic trichlorotin enolates or analogs and elec-
trophilic alkynyltin trichloride [7,8]. Yamamoto et al.
reported a Lewis acid promoted allylstannylation of
non-polar terminal alkynes [9]. All those reactions re-
quired electron-deficient alkynes as substrates and
highly nucleophilic organotin compounds as the
reagents. Recently, Shirakawa et al. have developed
transition metal-catalyzed carbostannylations of alky-
nes with 1-alkynyl-, 1-alkenyl-, and allyltributyltin
reagents [10–12]. They realized the reaction of neutral
1-alkynyl- and 1-alkenyltin reagents by the develop-
ment of electron-accepting ligands on palladium
[10,11,13,14]. Unlike alkyne carbostannylations, the
alkene counterpart has seldom been explored [7]. We
developed a palladium-catalyzed novel stereoselective
carbostannylation of norbornene utilizing an organotin
reagent containing carbon–tin–halogen inter-element
linkages. The present reaction provides the first exam-
ple of a palladium-catalyzed cis-carbostannylation of
1
. Introduction
Organotin reagents are useful because many of them
possess fairly stable carbon–tin bonds that can be
selectively activated by a variety of methods. Such
properties have enabled a number of selective syntheses
of complex organic molecules [1–3]. We have studied
the utility of carbon–tin–halogen inter-element link-
ages and found that carbon–tin bonds are useful for
palladium-catalyzed carbostannylation.
Carbometallation of alkenes is a useful two-carbon
homologation of organometallics [4,5]. It is desirable to
construct a carbon–tin bond according to this protocol.
Nevertheless, carbostannylation has been a rather unex-
plored reaction, in comparison with many other car-
bometallations as well as extensively studied stannyl-
metallations. The carbostannylation reaction was
first developed by Himbert, employing combinations
of nucleophilic organotin reagents and alkynes that
*
Corresponding author. Fax: +81-277-30-1285.
E-mail address: kosugi@chem.gunma-u.ac.jp (M. Kosugi).
0
022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00483-6

4
34
K. Fugami et al. / Journal of Organometallic Chemistry 611 (2000) 433–444
Table 1
allylic compounds with tin(II) salts in the presence of a
palladium catalyst [17,18]. Kurosawa et al. also re-
ported on a detailed mechanistic study [19]. Following
these precedents, we first attempted allylstannylation of
norbornene via in situ generation of allyltin trihalide in
DMF. Our first result was depressing, however. The
desired adduct was not obtained at all. Nevertheless,
further investigation revealed that the reaction is highly
dependent on the choice of the solvent. Thus the effects
of the solvent and temperature on the reaction between
norbornene and the reagent derived from allyl bromide
and tin(II) chloride were investigated. In order to facil-
itate the isolation and identification of the product, the
reaction was treated with ethylmagnesium bromide (Eq.
(2)). The results are summarized in Table 1.
Palladium-catalyzed carbostannylation of norbornene with allyl bro-
mide–tin(II) chloride
Run Solvent
Temperature (°C)
55
Time (h)
Yield (%) a
1
2
3
4
5
6
7
DMF
Dioxane 55
CH Cl2
Toluene 55
Toluene 55
Toluene rt
Toluene rt
11.5
11.5
11.5
3
1
11
0
33
89
98
47
59
93
reflux
2
48
a
Isolated yields based on tin(II) chloride used, assuming that 5
mol% is consumed to generate a catalytic Pd(0) species.
Table 2
Palladium-catalyzed carbostannylation of norbornene with allylic
compounds
(2)
DMF, which gave desirable results in the pioneers’
reaction systems, was not suitable for the present reac-
tion (run 1). Dioxane was not very good either (run 2).
On the other hand, excellent results were obtained in
non-coordinating solvents, such as dichloromethane
and toluene (runs 3, 4) [20]. Thus we chose toluene as
the solvent for further investigation. The reaction could
also be performed at room temperature (rt), although it
took a few days to go to completion (runs 6, 7).
We next explored the reagent precursor that can be
used for the allylstannylation. The results are summa-
rized in Table 2. The yields were excellent with allyl and
b-methallyl chloride (runs 1, 2). Not only allylic halides
but also allyl acetate and allyl phenyl ether could be
used, though the yields were not quite as high (runs 3,
a
Isolated yields.
non-polar carbon–carbon double bonds (Eq. (1))
[
15,16].
(
1)
4
). On the other hand, no reaction was observed when
iodobenzene was employed in place of allylic com-
pounds. Chloroacetone was not applicable either. Both
benzyl chloride and bromide gave 1,2-diphenylethane
as a sole product.
2
. Results and discussion
2
.1. Allylstannylation [15]
Scheme 1 depicts a plausible reaction pathway. The
catalytic palladium(0) species reacts with allyl chloride
and norbornene to form an intermediary complex A
Masuyama et al. have demonstrated that allylic tin
reagents can be generated in situ by treating various
Scheme 1. A plausible reaction pathway.

K. Fugami et al. / Journal of Organometallic Chemistry 611 (2000) 433–444
435
[
21,22]. Then it is transformed into the key intermediate
B by tin(II) chloride. This process might be reversible
19,23,24]. p-Allylpalladium chloride is indeed reported
The trend can be seen from Table 3. Crotyl and
a-methallyl chloride expressed analogous regioselectivi-
ties except when tin(II) bromide was used without
addition of triphenylphosphine (runs 1–8). This would
suggest that the reaction of both allylic compounds
proceeds through a common p-allylic palladium inter-
mediate. In general, new carbon–carbon bond forma-
tion took place at the less hindered allylic terminus to
give 2 when tin(II) chloride was used (runs 1, 5, 9, 13,
17, 23). On the contrary, exclusive production of 3 was
observed in the cases that crotyl or a-methallyl chloride
and tin(II) iodide were the reagent precursors (runs 4,
8). Also in the reactions of other allylic halides, forma-
tion of 3 predominated when tin(II) iodide was used
(runs 12, 16, 20). The use of tin(II) bromide generally
gave intermediate selectivity. The reactions with this
salt usually gave the highest total yields, especially
when 10 mol% of triphenylphosphine was added (runs
3, 7, 11, 15, 19). Forming a striking contrast to this, the
addition of the phosphine completely suppressed the
reaction when tin(II) chloride and iodide were used.
Tin(II) fluoride and acetate were not quite effective
(runs 21, 22). The reactions of methyl 4-bromocroto-
nate were different from those of other allylic halides:
by changing the tin(II) salt from chloride to bromide,
the yield decreased, though the adduct 2 was exclusively
obtained (run 24). Addition of the phosphine disturbed
the reaction (run 25). The adduct was not obtained
when tin(II) iodide was used either (run 26).
[
to add to norbornene to give the allylpalladation
product [25]. The process is not facile, however [26]. In
order to obtain the adduct in good yield, it is necessary
to replace the chloride ligand by a more electron-ac-
cepting ligand such as hexafluoroacetylacetonate via the
acetate [19,26–33]. Taking these facts into account, the
smooth isomerization of the intermediate B into C,
which is assumed to be the rate-determining step [34],
could be ascribable to a weakly s-donating and poten-
tially p-accepting character of the trichlorostannate lig-
and [24]. Finally, reductive elimination provides the
adduct D with a concomitant regeneration of the cata-
lytic palladium(0) species.
The complex B may also be in equilibrium with
allyltin trichloride under the reaction conditions [19].
Palladium-catalyzed reaction between allyl chloride and
tin(II) chloride in the absence of norbornene gave an
almost homogeneous solution in toluene, while tin(II)
chloride itself appears insoluble in this solvent. The
119
resulting reaction solution was investigated using Sn-
NMR. A sharp singlet was observed at l −25.1 ppm.
The corresponding solution obtained in THF showed a
signal at l −120.8 ppm. On the other hand, 0.5 mol
−
3
119
dm
THF solution of tin(II) chloride showed a Sn-
NMR signal at l −216.4 ppm. The appearance of the
new signals would suggest the formation of allyltin
trichloride or its complex. A significant difference of the
chemical shifts from that reported by Masuyama would
be attributable to the formation of a hypervalent struc-
ture of the allyltin species in such a strongly coordinat-
ing solvent as DMF [17,35]. The higher field shift
observed in THF might also reflect reversible formation
of such a species, though the solvent polarity would
also affect it to some extent. The present result was
surprising to us, because ultrasonic irradiation is neces-
sary for Masuyama’s carbonyl allylation in such a
solvent as toluene [35].
Regioselectivity was next studied with allylic reagents
with a substituent at the 1- or 3-position of the allylic
moiety (Eq. (3)). In the following studies, methylmag-
nesium iodide instead of ethylmagnesium bromide was
used to trap the products. The position of carbon–car-
bon bond formation can be altered by changing the
tin(II) salt [36].
Not only norbornene but also norbornadiene could
be allylstannylated (Eq. (4)). The results are indicated
in Table 4.
(4)
2.2. Arylstannylation
We next examined arylstannylation with aryltin
trichlorides. Following the failure in the attempt at in
situ generation of aryltin trihalides from the corre-
sponding aryl halides and tin(II) chloride, aryltin
trichlorides for the present study were prepared by
disproportionation between the corresponding te-
traaryltin and three molar equivalents of tin(IV) chlo-
ride (Eq. (5)) [37,38].
(
3)
(5)

4
36
K. Fugami et al. / Journal of Organometallic Chemistry 611 (2000) 433–444
Table 3
Allylstannylation with unsymmetrically substituted allylic compounds
Run
R
X
Y
Additive (10 mol%)
Products
Yield (%) a
2:3
Ratio b
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
Me
Me
Me
Me
Me c
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Br
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cl
Cl
Cl
Br
Br
Br
Br
Cl
Br
Br
I
Cl
Br
Br
I
Cl
Br
Br
I
Cl
Br
Br
I
61
74
97
34
60
40
79
42
82
68
91
21
79
71
95
34
54
71
95
15
19
21
66
13
0
100:0
15:85
25:75
0:100
100:0
50:50
27:73
0:100
100:0
40:60
28:72
23:77
100:0
43:57
47:53
48:52
100:0
95:5
75:25
86:14
78:22
PPh3
PPh3
PPh3
PPh3
PPh3
c
Me
86:14
84:16
84:16
Me c
Me c
Me
Me
Me
Me
Pr
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
80:20
80:20
83:17
Pr
Pr
Pr
Ph
Ph
Ph
Ph
Ph
75:25
73:27
84:16
Cl
Br
Br
I
77:23
73:27
76:24
38:62
37:63
100:0
F
Ph
OAc
Cl
Br
Br
I
31:6988:12
d
d
d
d
CO Me
100:0
100:0
2
CO Me
2
CO Me
PPh3
2
CO Me
0
2
a
b
c
Isolated yields based on tin(II) halide assuming that 5 mol% is consumed to generate Pd(0).
Diastereomer ratio of 3.
a-Methallyl chloride was used instead of crotyl chloride.
d
The ester moiety was converted to the corresponding tertiary alcohol by treatment with an excess of MeMgI when the allylstannylation was
terminated.
Table 4
Allylstannylation of norbornadiene
Run
R
X
Y
Additive (10 mol%)
Product
Yield (%) a
4:5
Ratio b
1
2
3
4
5
H
Br
Cl
Cl
Cl
Cl
Cl
Cl
Br
Br
I
58
62
53
74
33
Me
Me
Me
Me
100:0
100:0
38:62
0:100
PPh3
75:25
73:27
a
Isolated yields based on tin(II) halide assuming that 5 mol% is consumed to generate Pd(0).
Diastereomer ratio of 5.
b
With these reagents, oxidative addition of the car-
bon–tin bond to an ordinary palladium(0) species is
indispensable to the arylstannylation, while it may not
be essential to the allylstannylation discussed in the
previous section [10,11,13,14,39].
(6)

K. Fugami et al. / Journal of Organometallic Chemistry 611 (2000) 433–444
437
Table 5
Palladium-catalyzed p-tolylstannylation of norbornene
a
Run
Norbornene (mol equiv)
Catalyst (mol%)
Solvent
DMF
Temperature (°C)
Time (h)
Yield b (%)
Ratio 6a:7a
1
2
3
4
5
6
7
8
9
3.0
4.0
1.5
3.0
3.1
3.1
1.0
1.5
2.1
3.0
6.0
9.0
2.1
6.2
3.4
6.4
5.5
6.2
5
5
5
5
5
5
5
5
5
5
5
1
1
55
55
55
55
55
55
55
55
55
55
55
55
rt
2 c
2
8
2
2
2
2
9
2
2
2
2
72
2
8
63
44
46
85
82
61
65
77
79
83
84
75
84
0
88:12
29:71
45:55
46:54
39:61
38:62
72:28
69:31
65:35
68:32
65:35
71:29
69:31
67:33
(CH Cl)
2
2
THF
THF
CHCl3
Dioxane
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
10
11
12
13
14
15
16
17
18
d
5
55
55
55
55
55
0
5
5
5
2
e
11
24
96
11
70
87
98:2
95:5
80:20
e
e
a
b
c
Conditions are as described in the text unless otherwise noted.
Isolated yields after GPC separation based on the tin reagent used.
p-Tolyltrimethyltin was obtained in 65% yield.
d
e
Pd(dba)2 was used in place of PdCl (PhCN) .
2
2
Triphenylphosphine (10 mol%) was added to the reaction.
Basic aspects of the reaction were first explored using
p-tolyltin trichloride. The results are summarized in
Table 5.
triphenylphosphine (two molar equivalents) to the pal-
ladium catalyst had interesting effects on the reaction:
although the reaction was slowed down, prolonged
reaction provided the highest yield and selectivity for
the production of 6 (runs 16–18).
The stereochemistry of the product was elucidated by
an X-ray crystallographic analysis of the 2:1 adduct 7j
obtained by the reaction between phenyltin trichloride
and norbornene and subsequent treatment of the reac-
tion mixture with phenylmagnesium bromide. As
shown in Fig. 1, both of the norbornene-insertions
proceeded via an exo-cis fashion.
The reaction gave a mixture of 1:1 adduct 6 and 2:1
adduct 7 (Eq. (6)). Each product was obtained as a
single isomer. The stoichiometry between the tin
reagent and norbornene had no marked influence on
the product ratio (runs 3, 4 and runs 7–11). A signifi-
cant amount of the 2:1 adduct 7 was obtained even
when only one molar equivalent of norbornene was
used (run 7). No products via incorporation of the third
norbornene molecule were detected in any case even
when as much as nine molar equivalents of norbornene
were used (run 12). On the other hand, the results were
highly dependent on the solvent, although the causation
between them is unknown. The trend of the solvent
effect resembles that of allylstannylation, namely, the
reaction gave higher yields in less coordinating solvents
such as benzene, chloroform, and 1,2-dichloroethane
than in a highly coordinating solvent such as DMF
(
runs 1, 2, 5, 10). THF gave intermediate results (3, 4).
Dioxane, which is an ethereal solvent like THF but the
dielectric constant of which is as low as that of benzene,
gave a high yield (run 6). The amount of the catalyst
could be reduced to 1 mol% (run 12). Although it takes
longer, the reaction could be performed at room tem-
perature (run 13). Not only a palladium(II) complex
but also a palladium(0) complex was effective as a
catalyst precursor (run 14). The palladium catalyst was
indispensable to the reaction (run 15). An addition of
Fig. 1. The X-ray structure of 7j.

4
38
K. Fugami et al. / Journal of Organometallic Chemistry 611 (2000) 433–444
Scheme 2. A plausible reaction pathway.
Table 6
Palladium-catalyzed arylstannylation of norbornene
a
Run
Substituent on the Ar
Norbornene (mol equiv.)
Catalyst (mol%)
Time (h)
Yield (%) b
Ratio 6:7
1
2
3
4
5
6
7
8
9
m-CF3
m-F
m-Cl
p-Cl
p-F
6.0
6.0
6.0
6.0
3.9
6.0
6.0
6.0
5
1
1
1
1
1
1
1
5
2
5
5
2
2
2
2
2
2
2
24
2
2
73
84
87
82
90
83
83
24
85
60
63
84:16
79:21
77:23
72:28
77:23
77:23
65:35
67:33
54:46
75:25
67:33
H
p-Me
o-Me
p-OMe
H
c,d
c,d
1
1
0
1
6.0
6.0
p-Me
2
a
b
c
Conditions are as described in the text.
Isolated yields after GPC separation based on the tin reagent used.
The reaction mixture was treated by PhMgBr instead of MeMgI.
d
Compound numbers for products in runs 10 and 11: run 10, 6j and 7j; run 11, 6k and 7k.
Thus, the reaction pathway could be interpreted as
depicted in Scheme 2.
avoid steric interaction between the bridge methylenes
of both norbornene moieties.
The reaction did not proceed at all with the corre-
sponding tributyltin reagent, under the present condi-
tions. It would be reasonable to expect that oxidative
addition of not only aryltin trichlorides but also aryl-
tributyltins to the catalytic palladium(0) species takes
place [14,39]. The crucial difference between the
trichlorotin and tributyltin reagents would therefore lie
in the norbornene-insertion step. According to
Kurosawa’s report, the trichlorostannate ligand makes
palladium highly electrophilic, allowing more efficient
complexation with a nucleophilic alkene [19]. Thus the
electron-accepting character of the trichlorostannate
ligand must have played a decisive role in the present
reaction [24].
The reaction would be catalyzed by a palladium(0)
species, because the result with bis(dibenzylideneace-
tone)palladium(0) complex was similar to that with
dichlorobis(benzonitrile)palladium(II) (Table 5 runs
11,14). Thus the reaction is initiated by an oxidative
addition of aryltin trichloride to a catalytic palla-
dium(0) species. Subsequent arylpalladation of the car-
bon–carbon double bond generates the key
intermediate A. The following reductive elimination
affords the adduct I with concomitant regeneration of
the catalytic palladium(0) species. On the other hand,
the product II is formed when a further carbopallada-
tion of another norbornene molecule occurs prior to the
reductive elimination. According to the X-ray crystallo-
graphic analysis, the reaction of the second norbornene
proceeds in a regio- as well as stereoselective way to
The results with other aryltin trichlorides are given in
Table 6. The reaction was successful with a wide range
of aryltin reagents from that with electron-donating to

K. Fugami et al. / Journal of Organometallic Chemistry 611 (2000) 433–444
439
electron-withdrawing substituents. All the products ob-
3.1. Typical procedure for the allylstannylation of
norbornene
tained were single isomers, again. A certain degree of
correlation was observed between the electronic charac-
ter of the aromatic substituent and the product ratio,
namely, the more the substituent is electron donat-
ing, the higher the proportion of the 2:1 adduct 7
was.
To a solution (3.0 ml) of dichlorobis(benzoni-
trile)palladium (9.6 mg, 0.025 mmol) were added allyl
bromide (60 mg, 0.5 mmol), norbornene (141 mg, 1.5
mmol), and tin(II) chloride (95 mg, 0.5 mmol) in a 10
®
ml Pyrex tube equipped with a magnetic stirring bar
The observed dependence of the product distribution
on the aryl substituent might reflect the stability of the
key intermediate A. An intramolecular coordination in
under nitrogen, successively. The tube was cooled with
a liquid nitrogen bath and sealed under vacuum, then
heated at 55°C. The tube was then opened under nitro-
gen and the reaction mixture was treated with an
ethereal solution of ethylmagnesium bromide (0.95 mol
2
h fashion has been reported for structurally analogous
palladium iodide complexes with hydrogen or an elec-
tron-donating substituent on the aromatic ring [40,41].
This type of coordination should bring about certain
stabilization of the complex A. Thus, a more electron-
donating substituent is likely to impart more stability to
the corresponding intermediate A, and thus, more prob-
ability of its undergoing insertion of another norbor-
nene molecule to afford higher proportion of the
adduct II (Scheme 1).
−
3
dm , 4.5 mmol) at 0°C and stirred at rt for 1 h. The
crude product was obtained by quenching with water,
extraction with ether, and drying the organic layer over
anhydrous sodium sulfate. Silica-gel column chro-
matography after concentration afforded the desired
product, exo-cis-2-(2-propenyl)-3-triethylstannylbicyclo-
1
[2.2.1]heptane (1a) as a colorless oil. H-NMR (200
MHz, CDCl
1.05–2.21 (m, 12H), 4.95 (m, 2H), 5.75 (m, 1H). C-
NMR (CDCl ): l 1.82, 11.1, 29.7, 33.3, 35.0, 37.3, 40.1,
): l 0.80 (m, 6H), 1.17 (t, J=7.5 Hz, 9H),
3
1
3
In conclusion, palladium-catalyzed stereoselective
carbostannylation of norbornene that does not occur
with the corresponding tributyltins was realized by the
utilization of carbon–tin–halogen inter-element link-
ages. The present reaction furnishes not only a new
carbon–carbon bond but also a new carbon–tin bond
that may possess potential utility for further transfor-
mations [42,43].
3
119
40.9, 44.0, 46.2, 114.9, 138.6.
Sn-NMR (CDCl ): l
3
−10.6.
3.1.1. exo-cis-2-(2-Methyl-2-propenyl)-
3-triethylstannylbicyclo[2.2.1]heptane (1b)
1
Colorless oil. H-NMR (200 MHz, CDCl ): l 0.80
3
(
m, 6H), 1.17 (t, J=7.5 Hz, 9H), 1.03–2.24 (m, 15H),
13
3. Experimental
4.65 (s, 1H), 4.72 (s, 1H). C-NMR (CDCl ): l 1.85,
3
1
1.1, 22.5, 29.8, 33.4, 35.0, 37.5, 40.1, 41.0, 43.9, 48.1,
1
119
H (200 MHz) NMR spectra were recorded on a
111.0, 145.3. Sn-NMR (CDCl ): l −10.7 (s).
3
13
Varian Gemini 200 spectrometer. C (125.7 MHz) and
1
19
Sn (186.4 MHz) NMR spectra were recorded on a
1
13
JEOL JNM-a500 spectrometer. H and C chemical
shifts are referenced to internal tetramethylsilane ( H l
.00 ppm) and chloroform-d ( C l 77.00 ppm), respec-
tively.
3.1.2. exo-cis-2-(2-Butenyl)-3-trimethyl-
stannylbicyclo[2.2.1]heptane (2a)
1
13
1
0
Colorless oil. H-NMR (of a 75:25 mixture of geo-
1
19
Sn shifts are referenced to external te-
metrical isomers, 200 MHz, CDCl ): l 0.04 (s, 6.75H),
3
1
19
tramethyltin ( Sn l 0.00 ppm). Mass spectra were
measured at 70 eV on a Shimadzu QP2000A mass
spectrometer. IR spectra were recorded on a Perkin–
Elmer 1600 FT-IR spectrophotometer. The elemental
analyses were performed at the Technical Research
Center for Instrumental Analysis, Gunma University.
Gel permeation chromatography was performed on a
liquid chromatograph LC-08 (Japan Analytical Indus-
try Co., Ltd.) using JAIGEL-H. Melting points were
measured with a Yanaco-MP apparatus. Benzene, tolu-
ene, and 1,4-dioxane were distilled under an argon
atmosphere from freshly prepared sodium wire. Diethyl
ether (ether), THF, and hexane were distilled under an
argon atmosphere from sodium/benzophenone. Chloro-
form, DMF, DMSO, dichloromethane, and 1,2-
dichloroethane were distilled under an argon
atmosphere from calcium hydride.
0.07 (s, 2.25H), 0.95–2.22 (m,15H), 5.33–5.47 (m, 2H).
13
C-NMR (of the major isomer) (CDCl ): l −8.13,
3
18.0, 29.9, 33.3, 34.9, 38.8, 40.2, 40.8, 42.0, 46.8, 125.5,
131.1. Sn-NMR (CDCl ): l −12.8 (s).
119
3
3.1.3. exo-cis-2-(1-Methyl-2-propenyl)-3-
trimethylstannylbicyclo[2.2.1]heptane (3a)
1
Colorless oil. H-NMR (of a 75:25 mixture of
diastereomers, 200 MHz, CDCl ): l 0.02 (s, 6.75H),
0.07 (s, 2.25H), 0.96–2.29 (m,14H), 4.86–4.99 (m, 2H),
5.58–5.76 (m, 1H). C-NMR (CDCl ): l (−7.20),
−6.31, 12.5, 20.8 (21.1), 31.3, 32.5, 36.1, 39.2, 39.5
3
13
3
(40.1), 41.4, 42.4 (45.4), 52.3 (53.2) (112.8), 114.6, 144.6
1
3
( C chemical shifts in parentheses are assigned to
119
that of the minor isomer).
−11.8.
Sn-NMR (CDCl ): l
3

4
40
K. Fugami et al. / Journal of Organometallic Chemistry 611 (2000) 433–444
3.1.4. exo-cis-2-(2-Hexenyl)-3-trimethylstannylbicyclo-
3.1.10. exo-cis-2-(2-Butenyl)-3-
[
2.2.1]heptane (2b)
Colorless oil. H-NMR (200 MHz, CDCl ): l 0.05 (s,
trimethylstannylbicyclo[2.2.1]hept-5-ene (4b)
1
1
Colorless oil. H-NMR (200 MHz, CDCl ): l 0.08 (s,
3
3
9
0
1
1
H), 0.82 (t, J=7.2 Hz, 3H), 1.30 (q, J=7.4 Hz, 2H),
9H), 0.92–2.76 (m, 11H), 5.43 (m, 2H), 5.94 (m, 2H).
13
.93–2.16 (m, 14H). C-NMR (CDCl ): l −8.16,
3
3.7, 22.7, 29.9, 33.3, 34.8, 38.8, 40.0, 40.8, 42.0, 46.9,
3.1.11. exo-cis-2-(1-Methyl-2-propenyl)-3-
1
19
30.0, 191.0. Sn-NMR (CDCl ): l −12.7.
trimethylstannylbicyclo[2.2.1]hept-5-ene (5b)
3
1
Colorless oil. H-NMR (200 MHz, CDCl ): l 0.05 (s,
3
9
H), 1.00–2.98 (m, 10H), 4.85–5.01 (m, 2H), 5.57–5.91
3
.1.5. exo-cis-2-(1-Propyl-2-propenyl)-3-trimethyl-
(
m, 2H), 6.05 (m, 2H).
stannylbicyclo[2.2.1]heptane (3b)
1
Colorless oil. H-NMR (of a 75:25 mixture of
3.1.12. Palladium-catalyzed reaction between allyl
diastereomers, 200 MHz, CDCl ): l 0.01 (s, 6.75H),
0
5
diastereomer, CDCl ): l −6.10, 14.4, 19.3, 31.3, 32.4,
3
3
bromide and tin(II) chloride in the absence of
norbornene
.03 (s, 2.25H), 0.80–2.29 (m, 18H), 4.77–5.07 (m, 2H),
13
.32–5.66 (m, 1H).
C-NMR (of the major
The reaction was performed in the same way as
described in Section 3.1, except that norbornene was
excluded. After the precipitate of tin(II) chloride had
disappeared, the sealed tube was opened under argon
and the reaction solution was transferred to an NMR
tube under a stream of argon and investigated using
3
119
6.5, 39.2, 39.7, 41.3, 47.9, 50.6, 116.3, 142.3.
Sn-
NMR (CDCl ): l −12.8.
3
3.1.6. exo-cis-2-{(E)-3-Phenyl-2-propenyl}-3-
1
19
Sn-NMR.
.2. Typical procedure for the synthesis of tetraaryltin
In a 500 ml three-necked round-bottomed flask fur-
trimethylstannylbicyclo[2.2.1]heptane (2c)
1
Colorless oil. H-NMR (200 MHz, CDCl ): l 0.09 (s,
3
3
9
1
H), 1.06–2.25 (m, 12H), 6.18 (m, 1H), 6.34 (d, J=
6.2 Hz, 1H), 7.15–7.35 (m, 5H). C-NMR (CDCl ): l
1
3
3
−
1
8.07, 29.9, 33.3, 35.0, 38.8, 40.3, 40.9, 42.4, 46.8,
1
19
nished with a 300 ml dropping funnel, reflux condenser,
and magnetic stir bar were charged magnesium (11.6 g,
26.0, 126.9, 128.5, 130.5, 137.8. Sn-NMR (CDCl3):
l −12.2.
0
.48 mol) and ether (50 ml) under an argon atmo-
sphere. An ethereal solution (200 ml) of p-bromo-
toluene (50 g, 0.29 mol) was added so that gentle reflux
continued. After completion of the addition, the reac-
tion mixture was heated under reflux for 1 h, and then
tin tetrachloride (17.1 g, 66 mmol) was added dropwise
via a syringe at rt. The resulting gray suspension
refluxed overnight. Then it was poured into an ice-cold
3
.1.7. exo-cis-2-(1-Phenyl-2-propenyl)-3-
trimethylstannylbicyclo[2.2.1]heptane (3c)
1
Colorless oil. H-NMR (of a 77:23 mixture of
diastereomers, 200 MHz, CDCl ): l −0.33 (s, 2.07H),
3
0
0
5
.10 (s, 6.93H), 0.99–3.10 (m, 11H), 4.83–4.97 (m,
.46H), 5.09–5.13 (m, 1.54H), 5.59–5.66 (m, 0.23H),
.86–5.93 (m, 0.77H), 7.08–7.35 (m, 5H). C-NMR
13
−3
aqueous hydrochloric acid (1.0 mol dm , 400 ml).
(
CDCl ): l (−7.58), −5.97, 31.0 (31.3) (32.4), 32.5,
After stirring for 1 h, a white cake was collected by
filtration. The product was purified by recrystallization
from pyridine (15.7 g, 49%). Other tetraaryltins were
3
3
5
1
5.7 (35.8) (38.8), 39.8, 40.3 (40.5) (41.8), 41.9 (48.5),
0.9, 55.4 (56.8) (112.8), 116.2, 126.1 (126.6), 128.2,
13
synthesized analogously. Colorless crystals: m.p. 211°C.
28.4 (128.8) (129.0), 141.3 (142.8) (144.5), 145.2 ( C
1
H-NMR (200 MHz, CDCl ): l 2.35 (s, 12H), 7.21 (d,
chemical shifts in parentheses are assigned to the minor
isomer). Sn-NMR (CDCl ): l −10.6.
3
1
19
1
19
J=7.0 Hz, 8H), 7.48 (d, J=7.0 Hz, 8H). Sn-NMR
CDCl ): l −127.4.
3
(
3
3
.1.8. exo-cis-2-(4-Hydroxy-4-methyl-2-pentenyl)-3-
3
.2.1. Typical procedure for the synthesis of aryltin
trimethylstannylbicyclo[2.2.1]heptane (2d)
trichloride [37,38]
1
Colorless oil. H-NMR (200 MHz, CDCl ): l 0.05 (s,
3
In a 30 ml two-necked round-bottomed flask
equipped with a reflux condenser, rubber septum, and a
magnetic stir bar was charged tetra(p-tolyl)tin (8.37 g,
9H), 0.95–2.16 (m, 12H), 1.24 (s, 6H), 1.34 (s, 1H), 5.50
1
3
(m, 2H). C-NMR (CDCl ): l −8.26, 29.8, 33.2, 34.8,
3
3
8.7, 39.9, 40.7, 41.5, 46.5, 53.4, 70.6, 126.5, 138.6.
1
7.3 mmol). Tin(IV) chloride (6.20 ml, 53.0 mmol) was
1
19
Sn-NMR (CDCl ): l −12.4.
added under an argon atmosphere. The mixture was
heated at 150°C for 4 h. After cooling, fractional
distillation of the resulting colorless solution afforded
p-tolyltin trichloride as a colorless oil. Other aryltin
trichlorides were also prepared according to this proce-
3
3.1.9. exo-cis-2-(2-Propenyl)-3-trimethylstannylbicyclo-
[
2.2.1]hept-5-ene (4a)
1
Colorless oil. H-NMR (200 MHz, CDCl ): l 0.09 (s,
3
1
19
9H), 1.07–2.80 (m, 8H), 4.94–5.06 (m, 2H), 5.72–5.92
dure: b.p. 86.0–89.0°C/0.60 mmHg.
Sn-NMR
(
m, 1H), 5.95–6.09 (m, 2H).
(CDCl ): l −64.0.
3

K. Fugami et al. / Journal of Organometallic Chemistry 611 (2000) 433–444
441
3
.2.2. Arylstannylation of norbornene
In a 20 ml two-necked round-bottomed flask fur-
3.2.5. exo-cis-2-(m-Chlorophenyl)-3-(trimethylstannyl)-
bicyclo[2.2.1]heptane (6d)
1
nished with a reflux condenser and septum, dichloro-
bis(benzonitrile)palladium(II) (9.0 mg, 0.025 mmol) was
dissolved in a solvent (1 ml) at rt under an argon
atmosphere. To the solution was added a norbornene
solution in the same solvent (4 ml) via a syringe. Then,
aryltin trichloride (0.5 mmol) was added dropwise to
the resulting orange colored solution. The resulting
yellow solution was heated at 55°C for the time indi-
cated in Table 5. Then the reaction was cooled to rt and
H-NMR (200 MHz, CDCl ): l −0.29 (s, 9H),
3
1.31–1.53 (m, 3H), 1.62–1.96 (m, 4H), 2.32–2.55 (m,
13
2H), 3.05 (d), 6.99–7.22 (m, 4H). C-NMR (125.7
MHz, CDCl3): l −9.3, 30.9, 32.6, 37.6, 41.0, 41.8,
42.3, 50.7, 125.6, 125.8, 127.8, 129.8, 134.4, 150.7.
1
19
Sn-NMR (186.4 MHz, CDCl ): l −13.0. MS (m/z):
3
+
3
57 (37%), 355 (M −Me, 100%), 351 (37%), 261
43%), 165 (50%), 125 (25%), 67 (25%). Anal. Found:
C, 50.85; H, 6.11. Calc. for C H ClSn: C, 52.01; H,
(
16
23
−
3
treated by methylmagnesium iodide (1 mol dm
ether, 2.3 mmol) for 1 h. After treatment with 1 mol
in
6
.27%.
−
3
dm
poured into water and extracted with ether (three times,
0 ml each). The organic layer was combined and dried
hydrochloric acid, the reaction mixture was
3.2.6. exo-cis-2-[exo-cis-3-(m-Chlorophenyl)bicyclo-
[2.2.1]hept-2-yl]-3-trimethylstannylbicyclo[2.2.1]heptane
2
(
7d)
over anhydrous sodium sulfate. Volatiles were evapo-
rated off and the residue was submitted to silica-gel
column chromatography to exclude the materials other
than the desired adducts 6 and 7. The adducts 6 and 7
were separated from each other by GPC (chloroform).
1
H-NMR (200 MHz, CDCl ): l 0.11 (s, 9H), 0.36–
3
0
1
1
.53 (m, 1H), 0.80–0.96 (m, 1H), 0.98 (dm, J=9.2 Hz,
H), 1.06–1.66 (m, 11H) 1.72 (ddd, J=9.2, 5.5, 1.6 Hz,
H), 1.85 (ddd, J=10.2, 1.9, 1.9 Hz, 1H), 2.01 (br.d
J=3.9 Hz, 1H), 2.13 (br.d J=3.9 Hz, 1H), 2.39–2.43
m, 2H), 2.89 (br.d, J=9.2 Hz, 1H), 7.05–7.27 (m,
(
3.2.3. exo-cis-2-(p-Tolyl)-3-(trimethylstannyl)-
13
4
3
4
H). C-NMR (125.7 MHz, CDCl3): l −7.9, 30.3,
bicyclo[2.2.1]heptane (6a)
0.7, 31.1, 32.0, 36.6, 37.0, 38.1, 38.5, 40.9, 42.3, 43.6,
6.4, 53.2, 58.1, 125.6, 127.4, 129.0, 129.2, 133.7, 146.4.
1
H-NMR (200 MHz, CDCl ): l −0.30 (s, 9H),
3
1
2
.32–1.39 (m, 3H), 1.62–1.99 (m, 4 H), 2.31 (s, 3H),
+
MS (m/z): 451 (9%), 449 (M −Me, 24%), 197 (28%),
.41–2.62 (m, 2H), 3.05 (d, J=10.0 Hz, 1H), 7.01–7.10
1
7
65 (56%), 151 (30%), 128 (31%), 125 (39%), 95 (39%),
9 (47%), 67 (100%), 43 (30%).
1
3
(m, 4H). C-NMR (125.7 MHz, CDCl ): l −9.2, 20.7,
3
3
1
1
1
1.0, 32.7, 37.6, 40.9, 42.1, 43.0, 50.5, 127.4, 129.2,
35.1, 145.7.
1
19
Sn-NMR (186.4 MHz, CDCl ): l −
3
3.2.7. exo-cis-2-(p-Chlorophenyl)-3-(trimethylstannyl)-
4.56. IR (neat): w 2948 (s), 2868 (s), 1513 (s), 1472 (m),
451 (m), 1311 (w), 1295 (m), 1184 (m), 1172 (w), 1021
bicyclo[2.2.1]heptane (6e)
1
−
1
H-NMR (200 MHz, CDCl ): l 6.99–7.22 (m, 4H),
3
(
w), 968 (w), 841 (m), 812 (s), 762 (s), 709 (m) cm
.
+
3.05 (d, J=10.2 Hz, 1H), 2.32–2.55 (m, 2H), 1.62–1.96
MS (m/z): 335 (M −Me, 83%), 241 (53%), 239 (39%),
65 (37%), 128 (22%), 105 (100%), 91 (23%), 67 (34%).
Anal. Found: C, 57.57; H, 7.37. Calc. for C H Sn: C,
13
(
(
m, 4H), 1.31–1.53 (m, 3H), −0.29 (s, 9H). C-NMR
125.7 MHz, CDCl3): l −9.3, 30.9, 32.6, 37.6, 41.0,
1
1
7
26
4
1.8, 42.3, 50.7, 125.6, 125.8, 127.8, 129.8, 134.4, 150.7.
58.49; H, 7.51%.
119
Sn-NMR (186.4 MHz, CDCl ): l −13.0. MS (m/z):
3
+
3
57 (37%), 355 (M −Me, 100%), 351 (37%), 261
43%), 165 (50%), 125 (25%), 67 (25%). Anal. Found:
C, 51.66; H, 6.40. Calc. for C H ClSn: C, 52.01; H,
3.2.4. exo-cis-2-{exo-cis-3-(p-Tolyl)bicyclo[2.2.1]-
(
hept-2-yl}-3-trimethylstannylbicyclo[2.2.1]heptane (7a)
1
H-NMR (200 MHz, CDCl ): l −0.10 (s, 9H),
16 23
3
6
.27%.
0
1
3
7
.42–0.55 (m, 1H), 0.86–1.00 (m, 2H), 1.06–1.72 (m,
1H), 1.84–1.91 (m, 1H), 2.04–2.20 (m, 2H), 2.31 (s,
H), 2.39–2.40 (m, 2H), 2.88 (d, J=9.2 Hz, 1H),
3.2.8. exo-cis-2-{exo-cis-3-(p-Chlorophenyl)-
13
bicyclo[2.2.1]hept-2-yl}-3-trimethylstannylbicyclo[2.2.1]-
.02–7.12 (m, 4H). C-NMR (125.7 MHz, CDCl ): l
3
heptane (7e)
−
7.8, 30.4, 30.9, 31.2, 31.9, 36.6, 37.1, 38.2, 38.5, 41.0,
2.7, 43.9, 46.3, 53.0, 58.2, 128.5, 129.0, 134.8, 144.0.
1
H-NMR (200 MHz, CDCl ): l 0.11 (s, 9H),
4
3
1
19
0
1
.40–0.51 (m, 1H), 0.83–1.00 (m, 2H), 1.06–1.86 (m,
2H), 1.95–2.05 (m, 1H), 2.07–2.15 (m, 1H), 2.37–2.41
Sn-NMR (186.4 MHz, CDCl ): l −15.2. IR (neat):
3
w 2947 (s), 2867 (s), 1513 (s), 1473 (m), 1452 (s), 1377
w), 1309 (w), 1293 (m), 1255 (m), 1216 (m), 1186 (m),
141 (w), 1110 (m), 1042 (w), 1021 (m), 950 (w), 926
w), 908 (m), 891 (w), 842 (m), 811 (s), 758 (s), 701 (m)
(
1
(
(m, 2H), 2.88 (br.d J=9.2 Hz, 1H), 7.09–7.27 (m, 4H).
13
C-NMR (125.7 MHz, CDCl3): l −7.8, 30.3, 30.7,
31.2, 31.9, 36.5, 37.0, 38.1, 38.5, 40.9, 42.5, 43.7, 46.4,
−
1
+
cm . MS (m/z): 429 (M −Me, 44%), 279 (24%), 161
39%), 131 (31%), 105 (100%), 91 (28%), 67 (30%).
Anal. Found: C, 64.45; H, 8.20. Calc. for C H Sn: C,
52.8, 58.1, 127.9, 130.5, 131.1, 142.7. MS (m/z): 451
+
(
(11%), 449 (M −Me, 26%), 165 (72%), 151 (35%), 128
(28%), 125 (66%), 85 (40%), 79 (47%), 67 (100%), 43
(31%).
2
4
36
65.04; H, 8.19%.

4
42
K. Fugami et al. / Journal of Organometallic Chemistry 611 (2000) 433–444
3.2.9. exo-cis-2-(p-Fluorophenyl)-3-(trimethylstannyl)-
1H), 0.11 (s, 9H), 0.78–0.94 (m, 3H), 1.16–1.46 (m,
bicyclo[2.2.1]heptane (6f)
6H), 1.55–1.66 (m, 2H), 1.81–1.91 (m, 2H), 1.98–2.05
(m, 2H), 2.11–2.19 (m, 1H), 2.23 (s, 3H), 2.31–2.39 (m,
1H), 2.51 (m, 1H), 2.98 (br.d, J=9.4 Hz, 1H), 7.06–
1
H-NMR (200 MHz, CDCl ): l −0.30 (s, 9H),
3
1
2
2
.31–1.39 (m, 3H), 1.62–1.97 (m, 4H), 2.32–2.53 (m,
H), 3.06 (d, J=10.2 Hz, 1H), 6.94 (tt, J=8.8 Hz,
H), 7.11 (ddt, J=4.0 Hz, 2H). C-NMR (125.7 MHz,
13
7.15 (m, 3H), 7.30–7.34 (m, 1H). C-NMR (125.7
1
3
MHz, CDCl ): l −8.2, 20.5, 30.8, 30.9, 31.2, 32.4,
3
CDCl3): l −9.2, 31.0, 32.6, 37.5, 41.0, 44.2, 42.6, 50.2,
37.1, 37.2, 37.4, 38.2, 40.1, 40.9, 43.4, 45.9, 50.4, 55.7,
1
19
114.9, 115.3, 128.8, 128.9, 144.5, 163.6.
Sn-NMR
125.5, 125.7, 126.2, 129.6, 137.2, 142.3. MS (m/z): 429
+
+
(
186.4 MHz, CDCl ): l −13.7. MS (m/z): 339 (M −
(M −Me, 36%), 278 (22%), 161 (48%), 131 (33%), 105
3
Me, 97%), 337 (70%), 245 (69%), 165 (74%), 133 (33%),
(100%), 91 (32%), 79 (34%).
109 (100%), 67 (35%).
3.2.10. exo-cis-2-Phenyl-3-(trimethylstannyl)bicyclo-
3.2.14. exo-cis-2-(p-methoxyphenyl)-3-(trimethyl-
[
2.2.1]heptane (6g)
stannyl)bicyclo[2.2.1]heptane (6i)
1
1
H-NMR (200 MHz, CDCl ): l −0.31 (s, 9H),
H-NMR (200 MHz, CDCl ): l −0.31 (s, 9H),
3
3
1
2
.33–1.40 (m, 3H), 1.63–1.99 (m, 4H), 2.33–2.59 (m,
1.30–1.37 (m, 3H), 1.60–1.96 (m, 4H), 2.30–2.55 (m,
H), 3.09 (d, J=10.4 Hz, 1H), 7.13–7.30 (m, 5H).
2H), 3.02 (d, J=10.0 Hz, 1H), 3.78 (s, 3H), 6.79 (dt,
1
3
13
C-NMR (125.7 MHz, CDCl ): l −9.3, 31.0, 32.7,
J=9.0 Hz, 2H), 7.06 (dt, J=8.6 Hz, 2H). C-NMR
3
3
1
1
7.6, 41.1, 41.9, 42.7, 50.9, 125.7, 127.5, 127.6, 128.5,
(125.7 MHz, CDCl ): l −9.2, 31.0, 32.7, 37.5, 40.9,
42.2, 43.0, 50.1, 55.2, 113.8, 128.4, 141.1, 157.7. Sn-
3
1
19
119
28.6, 148.6.
Sn-NMR (186.4 MHz, CDCl ) l −
3
+
3.9. MS (m/z): 321 (M −Me, 77%), 227 (43%), 225
NMR (186.4 MHz, CDCl ): l −15.0. MS (m/z): 351
3
+
(
(
31%), 165 (54%), 135 (21%), 115 (24%), 91 (100%), 67
44%). Anal. Found: C, 57.57; H, 7.37. Calc. for
(M –Me, 100%), 257 (99%), 253 (42%), 201 (26%), 165
(33%), 121 (68%). Anal. Found: C, 55.68; H, 7.18. Calc.
C H Sn: C, 57.36; H, 7.22%.
for C H Sn: C, 55.93; H, 7.18%.
17 26
1
6
24
3.2.11. exo-cis-2-(exo-cis-3-Phenylbicyclo[2.2.1]-
hept-2-yl)-3-trimethylstannylbicyclo[2.2.1]heptane (7g)
3.2.15. exo-cis-2-{exo-cis-3-(p-methoxyphenyl)-
bicyclo[2.2.1]hept-2-yl}-3-trimethylstannylbicyclo[2.2.1]-
1
H-NMR (200 MHz, CDCl ): l 0.10 (s, 9H), 0.34–
3
0
1
2
.47 (m, 1H), 0.78–0.97 (m, 2H), 1.05–1.75 (m, 11H),
.81–1.92 (m, 1H), 2.00–2.19 (m, 2H), 2.41 (m, 2H),
.91 (d, J=9.2 Hz, 1H), 7.09–7.29 (m, 5H). C-NMR
heptane (7i)
1
H-NMR (200 MHz, CDCl ): l 0.10 (s, 9H), 0.42–
3
13
0.58 (m, 1H), 0.82–1.00 (m, 2H), 1.06–1.70 (m, 11H),
1.82–1.89 (m, 1H), 2.03–2.10 (m, 2H), 2.16–2.38 (m,
2H), 2.87 (d, J=9.0 Hz, 1H), 3.79 (s, 3H), 6.80 (dt,
(
125.7 MHz, CDCl ): l −7.8, 30.4, 30.8, 31.2, 31.9,
3
3
1
6.6, 37.0, 38.1, 38.5, 40.9, 42.4, 43.8, 53.3, 46.4, 58.1,
+
13
11.9, 125.5, 127.8, 129.2, 144.1. MS (m/z): 415 (M −
J=8.8 Hz, 2H), 7.12 (dt, J=8.8 Hz, 2H). C-NMR
Me, 83%), 265 (36%), 161 (45%), 143 (22%), 117 (40%),
1 (100%), 79 (31%), 67 (48%). Anal. Found: C, 64.72;
H, 8.18. Calc. for C H Sn: C, 64.36%, H: 7.99%.
(125.7 MHz, CDCl ): l −7.8, 30.3, 30.8, 31.3, 31.9,
3
9
36.5, 37.0, 38.2, 38.5, 40.9, 42.8, 43.9, 46.4, 52.6, 55.1,
+
58.2, 113.2, 130.0, 136.3, 157.6. MS (m/z): 460 (M ,
17
26
1
%), 445 (69%), 295 (41%), 161 (26%), 121 (100%), 91
3
.2.12. exo-cis-2-(o-Tolyl)-3-(trimethylstannyl)bicyclo-
(22%), 67 (24%). Anal. Found: C, 62.11; H, 7.98. Calc.
for C H Sn: C, 62.77; H, 7.90%.
[
2.2.1]heptane (6h)
24
36
1
H-NMR (200 MHz, CDCl ): l −0.34 (s, 9H),
3
1
2
.35–1.40 (m, 3H), 1.54–2.08 (m, 4H), 2.26 (s, 3H),
.34–2.55 (m, 2H), 3.14 (d, J=10.0 Hz, 1H), 6.99–7.26
3.2.16. exo-cis-2-Phenyl-3-(triphenylstannyl)-
1
3
(m, 4H). C-NMR (125.7 MHz, CDCl ): l −9.2, 20.3,
bicyclo[2.2.1]heptane (6j)
3
1
3
1
1.7, 32.4, 37.8, 41.1, 41.4, 42.0, 46.9, 125.3, 125.7,
26.3, 130.5, 135.8, 146.5.
H-NMR (200 MHz, CDCl ): l 1.35–1.88 (m, 6H),
3
119
Sn-NMR (186.4 MHz,
2.43–2.53 (m, 1H), 2.72 (dd, J=10.1, 2.5 Hz, 1H),
2.75–2.80 (m, 1H), 3.19 (d, J=10.1 Hz, 1H), 6.90–7.02
+
CDCl ): l −12.1. MS (m/z): 335 (M −Me, 87%),
2
1
3
13
41 (57%), 239 (43%), 165 (55%), 128 (23%), 115 (22%),
05 (100%), 91 (29%), 77 (21%), 67 (35%). Anal.
(m, 5H), 7.18–7.34 (m, 15H). C-NMR (50 MHz,
CDCl ): l 31.0, 32.7, 37.7, 41.3, 43.0, 44.8, 51.5,
3
Found: C, 57.10; H, 7.30. Calc. for C H Sn: C, 58.49;
H, 7.51%.
126.1, 127.7, 128.09, 128.13, 128.3, 128.37, 128.47,
17
26
119
128.56, 128.62, 136.9, 137.6, 140.6, 148.4. Sn-NMR
+
(
186.4 MHz, CDCl ): l 179.4. MS (m/z): 522 (M ,
3
+
3
[
(
.2.13. exo-cis-2-{exo-cis-3-(o-tolyl)bicyclo-
2.2.1]hept-2-yl}-3-trimethylstannylbicyclo[2.2.1]heptane
7h)
0.3%), 519 (0.2%), 445 (M −Ph, 0.4%), 351 (100%),
197 (24%), 120 (21%), 91 (34%), 67 (18%). Anal.
Found: C, 71.36; H, 5.80. Calc. for C H Sn: C, 71.43;
31
30
1
H-NMR (200 MHz, CDCl ): l −0.20–0.00 (m,
H, 5.80%.
3

K. Fugami et al. / Journal of Organometallic Chemistry 611 (2000) 433–444
443
3
.2.17. exo-cis-2-{exo-cis-3-Phenylbicyclo[2.2.1]-
0.81–1.10 (m, 3H), 1.10–1.58 (m, 10H), 1.61 (dd, J=
8.9, 5.9 Hz, 1H), 1.75 (dm, J=10.1 Hz, 1H), 1.90 (dd,
J=8.9, 5.9 Hz, 1H), 2.05 (dd, J=9.1, 2.1 Hz, 1H),
2.15 (br.d, J=3.8 Hz, 1H), 2.22 (br.s, 1H), 2.29 (s, 3H),
2.37 (br.s, 1H), 2.43 (br.d, J=3.8 Hz, 1H), 2.51 (d,
J=9.1 Hz, 1H), 6.84 (d, J=8.0 Hz, 2H), 6.96 (d,
hept-2-yl}-3-triphenylstannylbicyclo[2.2.1]heptane (7j)
1
H-NMR (200 MHz, CDCl ): l 0.46–0.61 (m, 1H),
3
0
1
2
.82–1.15 (m, 3H), 1.10–1.68 (m, 8H), 1.73–1.83 (m,
H), 1.87–2.01 (m, 1H), 2.07 (dd, J=9.2, 2.4 Hz, 1H),
.10–2.18 (m, 1H), 2.24–2.48 (m, 3H), 2.59 (d, J=9.0
Hz, 1H), 6.96–7.02 (m, 2H), 7.10–7.21 (m, 3H), 7.32–
J=8.0 Hz, 2H), 7.28–7.42 (m, 9H), 7.53–7.64 (m, 6H).
+
13
7
.42 (m, 9H), 7.56–7.64 (m, 6H). MS (m/z): 539 (M
Ph, 32%), 351 (100%), 347 (43%), 264 (29%), 197
41%), 117 (26%), 91 (55%), 67 (29%). Anal. Found: C,
3.66; H, 6.65. Calc. for C H Sn: C, 74.17; H, 6.55%.
C-NMR (50 MHz, CDCl ): l 20.8, 29.9, 30.6, 30.9,
3
−
(
31.9, 36.9, 37.4, 38.4, 38.5, 41.3, 42.7, 46.2, 46.9, 52.8,
60.7, 128.0, 128.4, 128.6, 128.7, 128.9, 134.8, 137.5,
+
7
141.0, 141.3. MS (m/z): 553 (M −Ph, 13%), 351
3
8
40
X-ray crystal structure analysis: the single crystals were
obtained by recrystallization from chloroform.
C H Sn, FW=615.42, monoclinic, space group P2 /n
(100%), 278 (78%), 211 (39%), 197 (34%), 161
(34%), 131 (31%), 120 (30%), 105 (98%), 91 (29%), 67
(42%). 4.
3
8
40
1
(
c4), a=10.014(2), b=10.253(2), c=15.650(3) A
,
,
3
i=117.91(2)°, V=1529.0(6) A
,
, Z=4, D =2.673 g
calc
−
3
−1
cm , v(Mo–K )=17.19 cm , number of reflections
Supplementary material
a
measured total 3925, unique 3720 (R =0.053), R=
int
0
.045, R =0.034 and GOF=1.43. All measurements
Complete lists of bond lengths and angles, hydrogen
atom coordinates and anisotropic thermal parameters
have been deposited at the Cambridge Crystallographic
Data Centre, CCDC no. 137553 for 7j. Copies of the
data can be obtained, free of charge, on application to
The Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (Fax: +44-1223-336033; e-mail: deposit@
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
w
were made at 2091°C on a Rigaku AFC7S diffrac-
tometer with graphite monochromated Mo–K radia-
,
tion (u=0.71069 A), using an ꢀ–2q scan technique to
a maximum 2q value of 55.0°. The data were corrected
for Lorentz and polarization effects. A correction for
secondary extinction was applied (coefficient 6.76500×
a
−
8
1
0
). The structure was solved by direct methods
(
(
SIR92) [44] and expanded using Fourier techniques
DIRDIF94) [45]. The non-hydrogen atoms were refined
anisotropically. Some hydrogen atoms were refined
isotropically, the rest were included in fixed positions.
The final cycle of full-matrix least-squares refinement
was based on 2257 observed reflections (I\3.00|(I))
and 461 variable parameters. The max./min. peaks on
the final difference Fourier map corresponded to 0.59/
Acknowledgements
Financial support by a Grant-in-Aid from the Min-
istry of Education, Science, Sports, and Culture of
Japan for Scientific Research on Priority Areas, The
Chemistry of Inter-element Linkage (No. 11120207 to
M. Kosugi) is gratefully acknowledged.
−
3
−
0.51 e A
formed using the TE
package of Molecular Structure Corporation (1985 and
,
, respectively. All calculations were per-
XSAN crystallographic software
1992).
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3.2.18. exo-cis-2-(p-Tolyl)-3-(triphenylstannyl)bicyclo-
[
2.2.1]heptane (6k)
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[
[
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3
[
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1
[
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H-NMR (200 MHz, CDCl ): l 0.51–0.67 (m, 1H),
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