Copper(I)-catalyzed tandem inter-intramolecular cyclization reactions of zirconacycles: Formation of highly substituted styrenes, vinylcyclohexadienes, and related compounds

Article abstract of DOI:10.1016/S0040-4020(01)01215-7

Copper(I)-catalyzed or mediated reactions of five-membered zirconacycles with propargyl or allyl halides afforded a variety of useful vinylated cyclic compounds, including highly substituted styrenes, vinylcyclohexadienes and methylenecycloheptadienes, vi

Full text of DOI:10.1016/S0040-4020(01)01215-7

TETRAHEDRON
Pergamon
Tetrahedron 58 +2002) 1107±1117
CopperꢀI)-catalyzed tandem inter±intramolecular cyclization
reactions of zirconacycles: formation of highly substituted
styrenes, vinylcyclohexadienes, and related compounds
Zhenfeng Xi,a,p Zhiping Li,a Chisato Umeda,b Hairong Guan,a Pixu Li,a Martin Kotorab
and Tamotsu Takahashib,p
aPeking University-Hokkaido University Joint Laboratory, Department of Chemistry, Peking University, Beijing 100871,
People's Republic of China
bCatalysis Research Center, Graduate School of Pharmaceutical Sciences, Hokkaido University, and CREST,
Japan Science and Technology Corporation +JST), Kita-Ku, Sapporo 060-0811, Japan
Received 28 May 2001; accepted 5 December 2001
AbstractÐCopper+I)-catalyzed or mediated reactions of ®ve-membered zirconacycles with propargyl or allyl halides afforded a variety of
useful vinylated cyclic compounds, including highly substituted styrenes, vinylcyclohexadienes and methylenecycloheptadienes, via tandem
inter±intramolecular allylation reactions. q 2002 Elsevier Science Ltd. All rights reserved.
1. Introduction
Tandem reactions are very attractive and useful approaches
for construction of cyclic compounds.1 We have been
interested in the development of novel methodologies for
cyclic compounds using zirconacycles, including zircon-
acyclopentadienes 1, zirconacyclopentenes 2 and zircon-
acyclopentanes
3,
as
reactive
organometallic
intermediates.2 One of the most interesting reactive
properties of such metallacycles is that there exist two
metal±carbon bonds in one molecule. Those two reactive
sites enable tandem reactions with bifunctional compounds
to give useful cyclic structures in a sequence. Recently, we
have demonstrated that, in the presence of a catalytic
amount or a stoichiometric amount of CuCl, tandem
inter±intramolecular reactions of zirconacyclopentadienes
1 with difunctional allyl halides such as 3,4-dichlorobutene
6 and 3-chloro-2-+chloromethyl)propene 5 to give vinyl-
cyclohexadienes and methylenecycloheptadienes, respec-
tively.3 These useful and interesting preliminary results
prompted us to further investigate the scope of the novel
transformation reaction. In this paper, we would like to
present our results in detail.
2. Results and discussion
2.1. Generation of highly substituted styrenes from the
reaction of zirconacyclopentadienes with 1,4-dibromo-2-
butyne mediated by copper salts
Styrene derivatives are important compounds for polymer
science, polymer industry,4 and syntheticorganicchemistry
as well.5 However, methodologies for the preparation of
styrene derivatives using transition metal complexes have
not been developed as such, although transition metal-
mediated cyclotrimerization of alkynes are extremely
important and useful reactions for the synthesis of various
6
aromaticcompounds. Yamamoto and co-workers recently
reported excellent methods for the formation of styrene
derivatives via Pd-catalyzed [412] homodimerization of
enynes.7 4,a-Disubstituted styrenes and 2,6-disubstituted
styrenes were synthesized via homodimerization of 2- and
4-substituted enynes, respectively.8
Keywords: vinylated cyclic compounds; ®ve-membered rings; six-
membered rings; seven-membered rings; zirconacycles; organocopper
compounds; transmetalation; tandem reactions; styrene derivatives.
Corresponding authors. Tel.: 181-11-706-2911; fax: 181-11-706-3274;
e-mail: tamotsu@cat.hokudai.ac.jp
p
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020+01)01215-7

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Z. Xi et al. / Tetrahedron 58+2002) 1107±1117
Scheme 3.
Scheme 1.
We have applied zirconacyclopentadienes which are
prepared in situ from two different or the same alkynes for
constructing highly substituted aromatic compounds.9±13
Recently, we reported when zirconacyclopentadienes were
treated with 2 equiv. of propargyl halides in the presence of
CuCl, 2,3-butadien-1-yl benzenes are formed.14 This
reaction prompted us to use 1,4-dihalo-2-butynes which
have two leaving groups and the corresponding reactive
positions. Results showed that highly substituted styrenes
were formed from the reaction of zirconacyclopentadienes
with 1,4-dibromo-2-butyne 4 in the presence of CuCl via a
tandem inter±intramolecular reaction sequence +Scheme 1).
with 1,4-dibromo-2-butyne in the presence of 2 equiv. of
CuCl +Scheme 3).
Although the yields of styrenes are not satisfactory enough,
to the best of our knowledge, the reaction represents the ®rst
example of intermolecular formation of highly substituted
styrenes from three molecules of alkynes +Scheme 4).
Firstly, we applied symmetrical zirconacyclopentadienes 1
for the reaction with 4. Reaction of zirconacyclopentadiene
1b +RˆPr) prepared in situ by dimerization of 4-octynes15
with 1 equiv. of 1,4-dibromo-2-butyne 4 in the presence of
2 equiv. of CuCl at 508C for 1 h afforded 2,3,4,5-tetra-
propylstyrene 7b in 60% yield. Similarly, styrene deriva-
tives 7c and 7a were obtained in 56 and 46% yields, from 1c
and 1a, respectively.
Scheme 4.
It is noteworthy that, under these reaction conditions, the
starting materials were all consumed. This result indicates
that an unclear reaction path is involved leading to unknown
products. Shown in Scheme 5 is a proposed reaction
mechanism for the formation of styrenes. We have reported
the ®rst example of transmetalation of zirconacyclopenta-
dienes 1 with CuCl to dicopper compounds.16 Reaction of
the dicopper compounds with 4 may lead to two inter-
mediates 8 and 9, via intermolecular coupling and via inter-
molecular g attack, respectively. Both 8 and 9 afford
intermediate 10 via an intramolecular reaction pattern.
Intermediate 10 ®nally transforms to the styrene derivatives
7. No evidence was observed for the formation of quino-
dimethene 11.
It is noteworthy that, besides 1,4-dibromo-2-butyne, 1,4-
dichloro-2-butyne could also be used, affording styrene
derivatives in similar yields. In the case of 1,4-dichloro-2-
butyne, a catalytic amount of CuCl +10 mol%) was also
effective for the styrene formation reaction, although the
yields were relatively lower.
As shown in Scheme 2, when the unsymmetrical zircon-
acyclopentadiene 1d9 prepared in situ from 2-butyne and
diphenylacetylene was treated in the presence of 2 equiv.
of CuCl with 1 equiv. of 1,4-dibromo-2-butyne, styrene
derivatives were formed as a mixture of two regioisomers
+7d and 7d0) in a ratio of 2:1 in 30% combined yield.
2.2. Generation of methylenecycloheptadienes and
vinylcyclohexadienes from the reaction of zircon-
acyclopentadienes with 3-chloro-2-ꢀchloromethyl)-
propene and 3,4-dichlorobutene mediated by copper
salts
Styrene derivatives 7e +RˆPh) and 7f +RˆPr) were formed
similarly in 47 and 35% yields, respectively, from the reac-
tion of the corresponding bicyclic zirconacyclopentadienes
Cyclic dienes are important compounds, for example, for
Scheme 2.

Z. Xi et al. / Tetrahedron 58+2002) 1107±1117
1109
Scheme 5.
the construction of more complexed polycyclic molecules.17
One possible and attractive approach to the synthesis of
cyclic dienes is the utilization of reactions of ®ve-membered
zirconacycles. In order to prepare cyclopentadienes from
®ve-membered zirconacycles, a one-carbon unit building
block is required. For six- and seven-membered cyclic
dienes, a two-carbon unit and a three-carbon unit building
block are necessary, respectively. We have reported
preparation of cyclopentadienes by copper-catalyzed
reaction of zirconacyclopentenes with acyl chlorides,18 by
the copper-catalyzed reaction of zirconacyclopentadienes
with ethyl propynoate,19 and by AlCl3-mediated deoxy-
genative cyclization of zirconacyclopentadienes with
aldehydes.20 In these reactions, acyl chlorides, ethyl
propynoates and aldehydes acted as one-carbon unit build-
ing blocks. Ethyl maleate and fumarate have been used as
two-carbon unit building blocks to react with zirconacyclo-
pentadienes to afford cyclohexadiene derivatives.11,21
Further investigation demonstrated that 3-chloro-2-+chloro-
methyl)propene 5 reacted with zirconacyclopentadienes 1 as
a three-carbon unit building block to form methylenecyclo-
heptadiene 12, while 3,4-dichlorobutene 6 as a two-carbon
unit building block to form vinylcyclohexadiene 13, via
tandem inter±intramolecular allylation +Scheme 6).
Results are summarized in Table 1. Generally, various
zirconacyclopentadienes +monocyclic, bicyclic, and
indenyl) could react with 5 or 6 in the presence of a catalytic
+10 mol%) or stoichiometric +2 equiv.) amount of CuCl. It is
interesting to note that in the cases of trimethylsilyl
substituted zirconacyclopentadienes, the desired product
13c could be obtained in a high yield only when a stoichio-
metricamount of CuCl was used. Use of a catalyticamount
+10 mol%) of CuCl either afforded very low yield of the
product +,10%) or the reaction did not proceed at all. In
the case of 13c, the carbon having a sterically hindered TMS
group has to attack the internal carbon. Therefore, the
catalytic reaction gave only low yield of the product. As
expected, the reaction of unsymmetrically substituted
zirconacyclopentadienes afforded a mixture of two regio-
isomers. In addition to 3,4-dichlorobutene 6, 1,4-dichloro-
2-butene could react also with a zirconacyclopentadiene to
afford the same product. For example, 13a was obtained in
58% yield from the reaction of zirconacyclopentadiene
1a with 1,4-dichloro-2-butene under similar reaction
conditions.
The mechanism of two types of reactions described earlier
is similar. As shown in Scheme 7, the essential step is
Scheme 6.

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Z. Xi et al. / Tetrahedron 58+2002) 1107±1117
Table 1. Reaction of zirconacyclopentadienes with 3,4-dichlorobutene and 3-chloro-2-+chloromethyl)propene in the presence of a catalytic amount of CuCl
Zirconacyclopentadiene 1
Product 12
Yield +%)a
Product 13
Yield +%)a
12a, 87 +62)
13a, 66 +59)
12b, 66 +47)
13b, 73 +61)b
12c +51)
13c +60)c
12d +50)
13d, 58 +37)c
12e, 71 +64)
13e +61)
12f, 79 +59)
13f, 57 +46)d
Otherwise noted, CuCl: 10 mol%, 3,4-dichlorobutene: 1 equiv. to zirconacylopentadiene; 3-chloro-2-+chloromethyl)propene: 1 equiv. to zirconacylopenta-
diene.
GC yields. Isolated yields are given in parenthese.
a
b
A mixture of two regioisomers in a ratio of 3:2.
2 equiv. of CuCl were used.
A mixture of two regioisomers in a ratio of 3:2.
c
d
Scheme 7.

Z. Xi et al. / Tetrahedron 58+2002) 1107±1117
1111
2.3. Tandem reaction of zirconacyclopentenes and
zirconacyclopentanes with 3,4-dichlorobutene and 3-
chloro-2-ꢀchloromethyl)propene
As we described earlier, tandem reactions of zirconacyclo-
pentadienes 1 with 4±6 afforded highly substituted styrenes
7, methylenecycloheptadiene derivatives 12 and vinylcyclo-
hexadiene derivatives 13, respectively. We then extended
the above useful protocol to other ®ve-membered zircona-
cycles, zirconacyclopentenes 2 and zirconacyclopentanes 3,
and found that the above reaction pattern works too. Results
are summarized in Table 2.
Scheme 8.
Monocyclic zirconacyclopentenes 2 +run 1 and 2, Table 2)
prepared in situ by our ethylene gas procedure9 reacted with
3,4-dichlorobutene 6 in the presence of a catalytic amount
of CuCl +10 mol%) at 508C for 1 h to afford 1,2-disubsti-
tuted-4-vinylcyclohexenes 19 in good yields as single
products +Scheme 9). 1,2-Dipropyl-4-vinylcyclohexene
19a and 1,2-diphenyl-4-vinylcyclohexene 19b were
obtained in 73 and 78% yields, respectively. Although the
reason is not clear, when the above monocyclic zircona-
cyclopentenes 2 were prepared in situ from our Cp2ZrCl2/
2EtMgBr/alkyne method,22 products 19a and 19b were
formed in low yields +,30%). In cases of bicyclic zircona-
cyclopentenes +run 3 and 4, Table 2), similar reactions
proceeded to form products 19c and 19d as mixtures of
diastereoisomers in good combined yields.
transmetalation of Zr±C bonds of zirconacyclopentadienes
to more reactive Cu±C bonds.2,16 The reaction mechanism
for the formation of vinylcyclohexadiene derivatives 13 is
shown in Scheme 8.
Lower yields in some cases may be attributed to the inter-
molecular side reactions which afford products with high
molecular weights. Indeed, formation of small amount of
polymericmaterials was observed. Generally, this protocol
offers a convenient and simple method for direct trans-
formations of zirconacyclopentadienes to six- or seven-
membered cyclic diene compounds.
Table 2. Reaction of zirconacyclopentenes and zirconacyclopentanes with 3,4-dichlorobutene in the presence of a catalytic amount of CuCl
Run
Zirconacyle 2, 3
T +8C)
t +h)
Product 19, 21
Yield +%)a
1
50
1
73 +55)
2
3
50
20
1
78 +55)
24
62 +56)b
4
5
6
20
50
50
24
3
71 +54)c
39 +35)d
41 +36)d
3
CuCl: 10 mol%, 3,4-dichlorobutene: 1 equiv. to zirconacycle.
GC yields. Isolated yields are given in parentheses.
a
b
A mixture of two stereoisomers in a ratio of 2:1.
A mixture of two stereoisomers in a ratio of 1.2:1.
A mixture of two isomers in a ratio of 2.5:1.
c
d

1112
Z. Xi et al. / Tetrahedron 58+2002) 1107±1117
preferential intermolecular allylation resulting in the
formation of unknown compounds rather than the intra-
molecular allylation that affords a seven-membered ring
compound.
Zirconacyclopentanes 3 reacted also in a similarly way with
3,4-dichlorobutene 6 to afford vinylated bicyclic products
21 as mixtures of diastereomers in good combined yields
+Scheme 11).2,23
Scheme 9.
The reaction mechanism of zirconacyclopentenes and
zirconacyclopentanes with 3,4-dichlorobutene is essentially
the same as that of zirconacyclopentadienes with 3,4-
dichlorobutene described previously. The only difference
between a zirconacyclopentene and a zirconacyclopenta-
diene is that there exist one Zr±sp2C bond and one
Zr±sp3C bond in a zirconacyclopentene, but two Zr±sp2C
bonds in a zirconacyclopentadiene. We have reported that
the Zr±sp2C bond, not the Zr±sp3C bond, is preferentially
transmetalated with CuCl.2,24 In fact, when the reaction of
monocyclic zirconacyclopentenes 2 with 3,4-dichloro-
butene 6 was carried out at room temperature instead of
508C, linear dienes 22 were obtained after hydrolysis
+Scheme 12). These results show that the Zr±sp2C bond of
zirconacyclopentenes is allylated ®rstly at room tempera-
ture. Therefore, a plausible reaction path is given in
Scheme 13.
Scheme 10.
Scheme 11.
3. Conclusion
We developed a new method for the construction of vinyl-
ated cyclic compounds from ®ve-membered zirconacycles
and polyfunctional dihalo reagents via tandem inter±intra-
molecular reactions catalyzed or mediated by copper+I)
salts. We demonstrated in this paper that a wide variety of
vinylated cyclic compounds +including Types I±V) could be
prepared by this useful protocol. 1,4-Dihalo-2-butyne
behaved as a two-carbon unit building block to afford highly
substituted styrene derivatives +Type I). In their CuCl-
catalyzed or mediated reactions with ®ve-membered
zirconacycles, 3,4-dichloro-1-butene or 1,4-dichloro-2-
butene, and 3-chloro-2-+chloromethyl)propene behaved as
two-carbon unit building blocks and three-carbon unit
building blocks, respectively, affording six-membered
and seven-membered vinylated cyclic compounds
+Types II±V).
Scheme 12.
A reaction of zirconacyclopentene 2e with 3-chloro-2-
+chloromethyl)propene 5 was also carried out in the
presence of a catalytic amount of CuCl +Scheme 10). The
reaction afforded the desired product 20 in a low yield
+38% by NMR). The low yield may be attributed to the
Scheme 13.

Z. Xi et al. / Tetrahedron 58+2002) 1107±1117
1113
NMR +CDCl3, Me4Si) d 1.11±1.28 +m, 12H), 2.62±2.73
+m, 8H), 5.22 +dd, Jˆ11.0, 1.8 Hz, 1H), 5.58 +dd, Jˆ17.4,
1.8 Hz, 1H), 7.01 +dd, Jˆ17.4, 11.0 Hz, 1H), 7.19 +s, 1H);
13C NMR +CDCl3, Me4Si) d 15.38, 15.54, 15.62, 15.88,
21.91, 21.98, 22.05, 25.76, 114.53, 124.23, 134.69,
135.90, 137.31, 139.70, 139.73, 139.78; HRMS calcd for
C16H24 216.1878, found 216.1891.
4.2.2. 2,3,4,5-Tetrapropyl-1-vinylbenzene ꢀ7b). Colorless
liquid, GC yield 60%, isolated yield 45% +244 mg). H
1
NMR +CDCl3, Me4Si) d 0.97±1.08 +m, 12H), 1.45±1.64
+m, 8H), 2.63±2.51 +m, 8H), 5.19 +dd, Jˆ11.0, 1.6 Hz,
1H), 5.55 +dd, Jˆ17.0, 1.6 Hz, 1H), 6.97 +dd, Jˆ17.0,
11.0 Hz, 1H), 7.15 +s, 1H); 13C NMR +CDCl3, Me4Si) d
14.51, 14.78, 15.00, 15.04, 24.50, 24.74, 24.75, 24.98,
31.60, 31.72, 31.87, 35.39, 114.32, 124.83, 134.56,
136.01, 136.09, 138.38, 138.74, 138.84; HRMS calcd for
C20H32 272.2504, found 272.2501.
4. Experimental
4.2.3. 2,3,4,5-Tetrabutyl-1-vinylbenzene ꢀ7c). Colorless
liquid, GC yield 56%, isolated yield 44% +286 mg). H
1
4.1. General
NMR +CDCl3, Me4Si) d 0.93±1.00 +m, 12H), 1.38±1.61
+m, 16H), 2.55±2.65 +m, 8H), 5.17 +dd, Jˆ10.8, 1.8 Hz,
1H), 5.54 +dd, Jˆ17.4, 1.8 Hz, 1H), 6.97 +dd, Jˆ17.4,
10.8 Hz, 1H), 7.15 +s, 1H); 13C NMR +CDCl3, Me4Si) d
13.87 +2C), 14.03 +2C), 23.09, 23.38, 23.55 +2C), 29.01
+2C), 29.13, 32.96, 33.41, 33.63, 33.83, 34.01, 114.24,
124.86, 134.54, 135.97, 136.07, 138.46, 138.64, 138.71;
HRMS calcd for C24H40 328.3130, found 328.3132.
Unless otherwise noted, all starting materials were com-
mercially available and were used without further puri®ca-
tion. All reactions involving organometallic compounds
were carried out under a positive pressure of dry N2 using
standard Schlenk techniques. Tetrahydrofuran +THF) was
re¯uxed and distilled from sodium benzophenone ketyl
under a nitrogen atmosphere. Zirconocene dichloride was
purchased from Aldrich Chemical Company, Inc., or from
Nichia Chemical Industries, Ltd. Japan. 3-Chloro-2-+chlor-
omethyl)propene was purchased from Aldrich Chemical
Company Inc. 3,4-Dichlorobutene was from TCI Company
Ltd. n-BuLi and EtMgBr were obtained from Kanto
Chemicals Company Ltd.
4.2.4. 2,3-Diphenyl-4,5-dimethyl-1-vinylbenzene ꢀ7d)
and 2,3-dimethyl-4,5-diphenyl-1-vinylbenzene ꢀ7d0).
Unsymmetrical zirconacyclopentadiene 1d was prepared
in situ according to a known procedure.9 The product was
obtained as a mixture of two regioisomers in a ratio of 2:1.
Colorless solid, GC yield 30%, isolated yield 18%
+101 mg). NMR data for the major: 1H NMR +CDCl3,
Me4Si) d 2.01 +s, 3H), 2.40 +s, 3H), 5.04 +dd, Jˆ11.1,
1.5 Hz, 1H), 5.63 +dd, Jˆ17.4, 1.5 Hz, 1H), 6.39 +dd,
Jˆ17.7, 11.1 Hz, 1H), 6.90±6.94 +m, 2H), 7.02±7.15 +m,
8H), 7.50 +s, 1H); 13C NMR +CDCl3, Me4Si) d 17.52, 20.77,
113.45, 125.31, 125.87, 125.91, 127.14 +2C), 127.37 +2C),
130.19 +2C), 130.81 +2C), 133.48, 134.53, 135.98, 136.04,
138.27, 139.84, 140.97, 141.68; NMR data for the minor: 1H
NMR +CDCl3, Me4Si) d 2.09 +s, 3H), 2.35 +s, 3H), 5.31 +dd,
Jˆ11.1, 1.5 Hz, 1H), 5.62 +dd, Jˆ17.4, 1.5 Hz, 1H), 6.39
+dd, Jˆ17.4, 11.1 Hz, 1H), 6.90±6.92 +m, 2H), 6.98±7.17
+m, 8H), 7.38 +s, 1H); 13C NMR +CDCl3, Me4Si) d 16.04,
18.18, 115.99, 125.25, 125.86, 126.16, 127.59 +2C), 127.79
+2C), 129.75 +2C), 130.58 +2C), 133.44, 135.17, 135.73,
135.97, 139.27, 140.18, 140.89, 142.15; HRMS calcd for
C22H20 284.1565, found 284.1578.
GC analysis was performed on a gas chromatograph
+Shimadzu GC-14B) equipped with a ¯ame ionization
detector using a fused silica capillary column +CBP1-
M25-025) and Shimadzu CR6A-Chromatopacintegrator.
GC yields were determined using suitable hydrocarbons as
internal standards. NMR spectra were recorded on a Bruker-
400 NMR spectrometer, or on a JEOL JNM-AL300 NMR
spectrometer.
4.2. A general procedure for the formation of highly
substituted styrenes 7 from the CuCl-mediated reaction
of zirconacyclopentadienes 1with 1,4-dibromo-2-butyne
4
To a THF +10 mL) solution of zirconacyclopentadiene 1
+2.0 mmol), prepared in situ from Cp2ZrBu2 +Negishi
reagent) +2.0 mmol) and the corresponding alkyne +for
mono-yne 4.0 mmol, for di-yne 2.0 mmol),15 were added
CuCl +4.0 mmol, 396 mg) and 1,4-dibromo-2-butyne
+2.0 mmol, 0.22 mL) at 2788C. The reaction mixture was
then warmed to 508C and stirred at 508C for 1 h. Hydrolysis
with 3N HCl followed by normal work up afforded crude
products, which were puri®ed by column chromatography
+silica gel, hexane).
4.2.5. 1,4-Diphenyl-2-vinyl-5,6,7,8-tetrahydronaphtha-
lene ꢀ7e). The molar ratio of zirconacyclopentadiene 1e to
1,8-diphenyl-1,7-octdiyne is 2:2. Colorless solid, GC yield
47%, isolated yield 44% +230 mg). 1H NMR +CDCl3,
Me4Si) d 1.62±1.66 +m, 4H), 2.40 +t, Jˆ5.7 Hz, 2H), 2.63
+t, Jˆ5.4 Hz, 2H), 4.98 +dd, Jˆ10.8, 1.5 Hz, 1H), 5.55 +dd,
Jˆ17.4, 1.5 Hz, 1H), 6.35 +dd, Jˆ17.1, 10.8 Hz, 1H), 7.17±
7.19 +m, 2H), 7.33±7.42 +m, 8H), 7.44 +s, 1H); 13C NMR
+CDCl3, Me4Si) d 22.84, 23.03, 28.84, 29.10, 113.51,
123.44, 126.74, 126.77 +2C), 128.03 +2C), 128.29 +2C),
4.2.1. 2,3,4,5-Tetraethyl-1-vinylbenzene ꢀ7a). Colorless
liquid, GC yield 46%, isolated yield 37% +160 mg). H
1

1114
Z. Xi et al. / Tetrahedron 58+2002) 1107±1117
129.27 +2C), 129.72, 133.26, 134.63, 135.59, 139.90,
140.02 +2C), 141.41, 142.05; HRMS calcd for C24H22
310.1722, found 310.1746.
4.3.4. 3-Methylene-1,5-diethyl-bicyclo-[5.4.0]-5,11-dode-
cadiene ꢀ12d). Kugelrohr distillation afforded 108 mg
+50%) of the title compound as a colorless liquid. 1H
NMR +CDCl3, Me4Si) d 0.98 +t, Jˆ7.5 Hz, 6H), 1.55±
1.65 +m, 4H), 2.16 +q, Jˆ7.5 Hz, 4H), 2.18±2.30 +m, 4H),
2.67 +m, 4H), 4.50±4.60 +m, 2H); 13C NMR +CDCl3, Me4Si)
d 14.02, 26.75, 27.11, 29.04, 40.96, 104.70, 133.69, 134.59,
160.62; HRMS calcd for C16H24 216.1877, found 216.1876.
4.2.6. 1,4-Dipropyl-2-vinyl-5,6,7,8-tetrahydronaphtha-
lene ꢀ7f). The molar ratio of zirconacyclopentadiene 1f to
4,10-tetradecadiyne is 2:2. Colorless liquid, GC yield 35%,
1
isolated yield 27% +132 mg). H NMR +CDCl3, Me4Si) d
0.89±1.03 +m, 6H), 1.44±1.65 +m, 4H), 1.76±1.79 +m, 4H),
2.49±2.61 +m, 4H), 2.72 +t, Jˆ4.4 Hz, 4H), 5.21 +dd,
Jˆ10.8, 1.8 Hz, 1H), 5.56 +dd, Jˆ17.1, 1.5 Hz, 1H), 6.99
+dd, Jˆ17.4, 10.8 Hz, 1H), 7.15 +s, 1H); 13C NMR +CDCl3,
Me4Si) d 14.46, 14.75, 22.84, 23.22, 23.26, 23.36, 26.82,
27.06, 30.73, 35.06, 114.50, 123.89, 133.89, 135.02, 135.09,
135.75, 136.08, 138.39; HRMS calcd for C18H26 242.2035,
found 242.2045.
4.3.5. 1,5-Diphenyl-3-methylene-bicyclo-[5.4.0]-5,11-dode-
cadiene ꢀ12e). White solid, GC yield 71%, isolated yield
1
64% +201 mg). H NMR +CDCl3, Me4Si) d 1.55±1.65 +m,
4H), 2.25±2.35 +m, 4H), 3.17 +s, 4H), 4.55±4.65 +m, 2H),
7.15±7.35 +m, 10H); 13C NMR +CDCl3, Me4Si) d 27.30,
31.20, 42.73, 106.86, 126.18, 127.95, 128.56, 134.67,
137.01, 143.37, 157.97; HRMS calcd for C24H24
312.1877, found 312.1884.
4.3. A general procedure for the formation of methyl-
enecycloheptadiene derivatives 12 from the CuCl-
catalyzed reaction of zirconacyclopentadienes 1with 3-
chloro-2-ꢀchloromethyl)propene 5
4.3.6. 5,7-Dihydro-6-methylene-8,9-diethylbenzocyclo-
heptene ꢀ12f). The indenyl zirconacyclopentadiene 1j was
prepared according to a known method.25 Colorless liquid,
GC yield 79%, isolated yield 59% +157 mg). 1H NMR
+CDCl3, Me4Si) d 0.90 +t, Jˆ7.6 Hz, 3H), 1.09 +t,
Jˆ7.6 Hz, 3H), 2.29 +q, Jˆ7.6 Hz, 2H), 2.55 +q,
Jˆ7.6 Hz, 2H), 2.57 +s, 2H), 3.31 +s, 2H), 4.65 +dt, Jˆ1.6,
1.3 Hz, 1H), 4.71 +dt, Jˆ1.6, 1.3 Hz, 1H), 7.10±7.30 +m,
4H); 13C NMR +CDCl3, Me4Si) d 13.82, 14.18, 25.35, 27.24,
40.20, 41.80, 106.05, 126.13, 126.18, 126.57, 128.23,
134.66, 136.55, 139.26, 141.65, 156.13; HRMS calcd for
C16H20 212.1565, found 212.1563.
To a zirconacyclopentadiene 1 in THF +5 mL), prepared in
situ from Cp2ZrBu2 +Negishi reagent) +1.0 mmol) and the
corresponding alkyne +for mono-yne 2.0 mmol, for di-yne
1.0 mmol),15 were added CuCl +0.1 mmol) and 3-chloro-2-
+chloromethyl)propene +1.0 mmol) at room temperature.
After being stirred at room temperature for 1±6 h till the
starting material was consumed, the reaction mixture was
hydrolyzed with 3N HCl followed by normal work up.
Evaporation in vacuo afforded crude products, which
were puri®ed by column chromatography or Kugelrohr
distillation.
4.4. A general procedure for the formation of vinylcyclo-
hexadiene derivatives 13 from the CuCl-catalyzed
reaction of zirconacyclopentadienes 1with 3,4-dichloro-
butene 6 and 1,4-dichloro-2-butene
4.3.1. 6-Methylene-1,2,3,4-tetraethyl-1,3-cycloheptadiene
ꢀ12a). Kugelrohr distillation afforded 135 mg +62%) of the
1
title compound as a colorless liquid, GC yield 87%. H
To a THF solution +5 mL) of zirconacyclopentadiene 1
+1.0 mmol) were added 3,4-dichlorobutene +1.0 mmol) and
CuCl +10 mg, 0.1 mmol). The reaction mixture was stirred
at room temperature or 08C till the starting material was
consumed. The reaction was then quenched with 3N HCl,
and extracted with hexane. Organic layers were collected,
washed with brine, dried over MgSO4, and concentrated in
vacuo. Products were isolated by Kugelrohr distillation or
column chromatography.
NMR +CDCl3, Me4Si) d 0.88 +t, Jˆ7.5 Hz, 6H), 1.01 +t,
Jˆ7.5 Hz, 6H), 2.10±2.20 +m, 8H), 2.66 +br, 4H), 4.55±
4.60 +m, 2H); 13C NMR +CDCl3, Me4Si) d 13.92, 14.19,
21.86, 27.01, 40.81, 104.94, 135.92, 136.85, 160.43;
HRMS calcd for C16H26 218.2035, found 218.2032.
4.3.2. 1,2-Diphenyl-6-methylene-3,4-diethyl-1,3-cyclo-
heptadiene ꢀ12b). Column chromatography on silica gel
+hexane/diethyl etherˆ99:1) afforded 147 mg +47%) of the
1
title compound as a colorless liquid, GC yield 66%. H
4.4.1. 6-Ethenyl-1,2,3,4-tetraethyl-1,3-cyclohexadiene
ꢀ13a). Kugelrohr distillation afforded 128 mg +59%) of the
NMR +CDCl3, Me4Si) d 0.85 +t, Jˆ7.6 Hz, 3H), 1.14 +t,
Jˆ7.6 Hz, 3H), 1.90±2.05 +m, 2H), 2.32 +q, Jˆ7.6 Hz,
2H), 2.99 +br, 2H), 3.22 +br, 2H), 4.52±4.58 +m, 1H),
4.65±4.70 +m, 1H), 6.85±7.15 +m, 10H); 13C NMR
+CDCl3, Me4Si) d 13.82, 14.18, 22.70, 27.19, 40.88,
43.65, 106.99, 125.84, 125.93, 127.44, 127.55, 130.28,
129.56, 136.53, 139.19, 139.32, 140.03, 140.50, 143.20,
158.58; HRMS calcd for C24H26 314.2035, found 314.2024.
1
title compound as a colorless liquid, GC yield 66%. H
NMR +CDCl3, Me4Si) d 0.92 +t, Jˆ7.6 Hz, 3H), 0.95 +t,
Jˆ7.6 Hz, 3H), 0.97 +t, Jˆ7.6 Hz, 3H), 1.02 +t, Jˆ7.6 Hz,
3H), 1.75±2.40 +m, 10H), 2.45±2.55 +m, 1H), 4.83 +dd,
Jˆ10.5, 2.2 Hz, 1H), 4.95 +ddd, Jˆ17.3, 2.0, 0.9 Hz, 1H),
5.72 +ddd, Jˆ17.2, 9.9, 8.1 Hz, 1H); 13C NMR +CDCl3,
Me4Si) d 13.00, 14.82, 15.35, 15.42, 20.32, 20.72, 24.95,
26.48, 34.10, 41.62, 113.16, 130.29, 131.95, 133.16, 134.91,
139.79; HRMS calcd for C16H26 218.2033, found 218.2034.
4.3.3. 1,4-Bisꢀtrimethylsilyl)-6-methylene-2,3-dimethyl-
1,3-cycloheptadiene ꢀ12c). Kugelrohr distillation afforded
142 mg +51%) of the title compound as a colorless liquid. 1H
NMR +CDCl3, Me4Si) d 0.25 +s, 18H), 1.84 +s, 6H), 2.78 +br,
4H), 4.70±4.73 +m, 2H); 13C NMR +CDCl3, Me4Si) d 0.92,
20.16, 39.39, 105.91, 134.86, 149.13, 159.91; HRMS calcd
for C16H30Si2 278.1886, found 278.1894.
4.4.2. 6-Ethenyl-1,2-diphenyl-3,4-diethyl-1,3-cyclohexa-
diene and 5-ethenyl-1,2-diphenyl-3,4-diethyl-1,3-cyclo-
hexadiene ꢀ13b). Column chromatography on silica gel
+hexane) afforded 191 mg +61%) of a mixture of the title
compounds +3:2) as colorless liquid, GC yield 73%. Major

Z. Xi et al. / Tetrahedron 58+2002) 1107±1117
1115
isomer: 1H NMR +CDCl3, Me4Si) d 0.70 +t, Jˆ7.4 Hz, 3H),
1.06 +t, Jˆ7.5 Hz, 3H), 1.80±2.50 +m, 5H), 2.65±2.85 +m,
1H), 2.95±3.05 +m, 1H), 5.00±5.30 +m, 2H), 6.05 +ddd,
Jˆ17.4, 10.0, 7.5 Hz, 1H), 6.80±7.50 +m, 10H); 13C NMR
+CDCl3, Me4Si) d 12.76, 14.73, 21.30, 26.55, 34.34, 44.56,
114.76, 125.37, 125.87, 127.18 +2C), 127.37 +4C), 128.76
+2C), 132.52, 133.07, 134.70, 137.93, 140.02, 140.66,
14.31, 20.58, 26.91, 34.23, 43.10, 115.00, 122.86, 125.81,
126.62, 126.92, 130.71, 135.38, 135.60, 137.53, 140.86.
Minor isomer: 1H NMR +CDCl3, Me4Si) d 1.14 +t,
Jˆ7.3 Hz, 3H), 1.15 +t, Jˆ7.5 Hz, 3H), 2.22±2.30 +m,
2H), 2.50±2.60 +m, 2H), 2.72 +dd, Jˆ14.9, 2.7 Hz, 1H),
2.80±2.90 +m, 1H), 3.03 +dd, Jˆ14.9, 6.5 Hz, 1H), 4.85±
5.00 +m, 2H), 5.65 +ddd, Jˆ17.3, 9.8, 7.7 Hz, 1H), 7.10±
7.41 +m, 4H); 13C NMR +CDCl3, Me4Si) d 14.08, 14.34,
20.84, 25.24, 35.08, 41.89, 114.12, 122.51, 125.73,
127.97, 128.75, 131.64, 134.11, 135.29, 138.95, 139.07;
HRMS calcd for C16H20 212.1564, found 212.1567.
1
142.96. Minor isomer: H NMR +CDCl3, Me4Si) d 0.72 +t,
Jˆ7.4 Hz, 3H), 1.13 +t, Jˆ7.5 Hz, 3H), 1.80±2.50 +m, 5H),
2.65±2.85 +m, 1H), 2.95±3.05 +m, 1H), 4.95±5.51 +m, 2H),
5.96 +ddd, Jˆ17.4, 10.0, 7.5 Hz, 1H), 6.80±7.50 +m, 10H);
13C NMR +CDCl3, Me4Si) d 14.73, 14.89, 21.58, 25.06,
36.76, 41.24, 114.01, 125.34, 125.90, 127.18 +2C), 128.36
+2C), 128.76 +2C), 131.17, 134.01, 136.67, 136.88, 138.78,
140.43, 143.52; HRMS calcd for C24H26 314.2033, found
314.2034.
4.5. Preparation of 1,2-disubstituted-4-vinylcyclohexene
19a,b from CuCl-catalyzed monocyclic zirconacyclo-
pentenes 2 and 3,4-dichloro-1-butene 6
Zirconacyclopentenes were prepared in situ by our pro-
cedure.9 To the THF +5 mL) solution of thus prepared
zirconacyclopentene +1.0 mmol) were added 3,4-dichloro-
butene +1.0 mmol) and CuCl +0.1 mmol) at room tempera-
ture. After being stirred at 508C for 1 h, the reaction mixture
was hydrolyzed with 3N HCl, followed by normal work up.
4.4.3.
2-Ethenyl-1,4-bisꢀtrimethylsilyl)cyclohexadiene
ꢀ13c). Column chromatography on silica gel +hexane)
afforded 167 mg +60%) of the title compound as a colorless
liquid. 1H NMR +CDCl3, Me4Si) d 0.14 +s, 9H), 0.17 +s, 9H),
1.88 +d, Jˆ2.5 Hz, 3H), 1.92 +s, 3H), 2.08±2.17 +m, 1H),
2.24 +dd, Jˆ16.3, 0.9 Hz, 1H), 2.70±2.78 +m, 1H), 4.82 +d,
Jˆ10.2 Hz, 1H), 4.88 +d, Jˆ17.2 Hz, 1H), 5.64 +ddd,
Jˆ17.2, 10.2, 7.1 Hz, 1H); 13C NMR +CDCl3, Me4Si) d
20.22, 0.47, 19.57, 19.90, 32.94, 39.06, 113.22, 130.32,
134.27, 139.71, 142.71, 143.37; HRMS calcd for
C16H30Si2 278.1884, found 278.1888.
4.5.1. 1,2-Dipropyl-4-vinylcyclohexene ꢀ19a). Column
chromatography on silica gel +hexane) afforded 210 mg
+55%) of the title compound as a colorless liquid, GC
1
yield 73%. H NMR +CDCl3, Me4Si) d 0.90 +t, Jˆ7.1 Hz,
3H), 0.91 +t, Jˆ7.2 Hz, 3H), 1.29±1.43 +m, 6H), 1.74±1.87
+m, 2H), 1.96±2.26 +m, 7H), 4.94 +ddd, Jˆ10.0, 1.1, 1.1 Hz,
1H), 5.02 +ddd, Jˆ17.0, 1.6, 1.6 Hz, 1H), 5.85 +ddd, Jˆ17.1,
10.2, 6.6 Hz, 1H); 13C NMR +CDCl3, Me4Si) d 14.23 +2C),
21.64, 21.70, 29.12 +2C), 34.98, 35.16, 35.39, 38.44, 112.10,
129.21, 129.98, 144.11; HRMS calcd for C14H24 192.1878,
found 192.1880.
4.4.4.
2-Ethenyl-1,4-diethyl-2,3,5,6,7,8-hexahydro-
naphthalene ꢀ13d). 2 equiv. of CuCl were used. Kugelrohr
distillation afforded 80 mg +37%) of the title compound as a
colorless liquid, GC yield 58%. 1H NMR +CDCl3, Me4Si) d
0.94 +t, Jˆ7.6 Hz, 3H), 0.98 +t, Jˆ7.6 Hz, 3H), 1.40±2.60
+m, 15H), 4.80±5.01 +m, 2H), 5.74 +ddd, Jˆ17.5, 9.7,
7.9 Hz, 1H); 13C NMR +CDCl3, Me4Si) d 12.15, 13.73,
24.11 +2C), 24.39, 25.87, 25.92, 26.15, 34.18, 41.98,
113.04, 127.32, 128.49, 128.88, 133.09, 140.04; HRMS
calcd for C16H24 216.1877, found 216.1871.
4.5.2. 1,2-Diphenyl-4-vinylcyclohexene ꢀ19b). Column
chromatography on silica gel +hexane) afforded 286 mg
+55%) of the title compound as a colorless liquid, GC
yield 78%. 1H NMR +CDCl3, Me4Si) d 1.58±1.68 +m,
2H), 1.95±2.02 +m, 2H), 2.29±2.36 +m, 2H), 2.58±2.60
+m, 1H), 5.01 +ddd, Jˆ10.0, 1.4, 1.4 Hz, 1H), 5.11 +ddd,
Jˆ17.3, 1.5, 1.5 Hz, 1H), 5.94 +ddd, Jˆ17.1, 10.7, 6.7 Hz,
1H), 6.96±6.99 +m, 5H), 7.01±7.11 +m, 5H); 13C NMR
+CDCl3, Me4Si) d 28.87, 31.58, 37.59, 38.09, 112.90,
125.77 +2C), 127.58 +2C), 127.62 +2C), 128.96 +2C),
128.99 +2C), 133.91, 134.63, 143.05, 143.34, 143.39;
HRMS calcd for C20H20 260.1565, found 260.1561.
4.4.5. 2-Ethenyl-1,4-diphenyl-2,3,5,6,7,8-hexahydro-
naphthalene ꢀ13e). Column chromatography on silica gel
+hexane) afforded 190 mg +61%) of the title compound as a
yellow liquid. H NMR +CDCl3, Me4Si) d 1.40±1.75 +m,
4H), 2.10±2.30 +m, 2H), 2.35±2.65 +m, 3H), 3.85±4.10 +m,
2H), 4.90±5.10 +m, 2H), 5.94 +ddd, Jˆ17.4, 10.2, 7.2 Hz,
1H), 7.10±7.50 +m, 10H); 13C NMR +CDCl3, Me4Si) d
23.76, 23.86, 27.53, 27.86, 36.56, 43.97, 114.36, 126.13,
127.86 +2C), 127.97 +2C), 128.38 +2C), 128.88 +2C),
129.15, 131.52, 132.40, 133.35, 139.07, 142.29, 143.02;
HRMS calcd for C24H24 312.1877, found 312.1878.
1
4.6. Preparation of bicyclic compounds 19c,d from the
CuCl-catalyzed reaction of bicyclic zirconacyclo-
pentenes 2 with 3,4-dichlorobutene 6
4.4.6. 2-Ethenyl-3,4-diethyl-1,2-dihydronaphthalene and
1-ethenyl-3,4-diethyl-1,2-dihydronaphthalene ꢀ13f). The
indenyl zirconacyclopentadiene 1j was prepared according
to a known method.24 Column chromatography on silica gel
+hexane) afforded 98 mg +46%) of a mixture of the title
To a THF +5 mL) solution of bicyclic zirconacyclopentene
+1.0 mmol) prepared in situ from the reaction of Cp2ZrBu2
+1.0 mmol) and the corresponding enyne +1.0 mmol), were
added 3,4-dichlorobutene +1.1 mmol) and CuCl +0.1 mmol)
at 08C. The reaction mixture was stirred at room tempera-
ture for 24 h. Normal work up followed by column chroma-
tography on silica gel +hexane) afforded the products.
1
compounds +3:2) as a colorless liquid. Major isomer: H
NMR +CDCl3, Me4Si) d 1.09 +t, Jˆ7.6 Hz, 3H), 1.11 +t,
Jˆ7.5 Hz, 3H), 2.15±2.30 +m, 3H), 2.41 +dd, Jˆ16.0,
6.4 Hz, 1H), 2.57 +q, Jˆ7.5 Hz, 2H), 3.35±3.45 +m, 1H),
5.00±5.10 +m, 2H), 5.98 +ddd, Jˆ16.8, 10.2, 8.0 Hz, 1H),
7.10±7.41 +m, 4H); 13C NMR +CDCl3, Me4Si) d 12.84,
4.6.1. 2-Phenyl-4-ethenylbibyblo[4.3.0]non-1-ene ꢀ19c).
A 2:1 mixture of diasteroisomers, colorless liquid, GC
1
yield 62%, isolated yield 56% +125 mg). Major isomer: H

1116
Z. Xi et al. / Tetrahedron 58+2002) 1107±1117
1
colorless liquid, GC yield 39%. Major isomer: H NMR
NMR +CDCl3, Me4Si) d 1.00±1.15 +m, 2H), 1.50±1.75 +m,
2H), 1.90±2.35 +m, 5H), 2.40±2.55 +m, 1H), 2.65±2.75 +m,
2H), 4.90±5.10 +m, 2H), 5.99 +ddd, Jˆ17.0, 10.4, 6.2 Hz,
1H), 7.2±7.4 +m, 5H); 13C NMR +CDCl3, Me4Si) d 23.26,
29.42, 33.09, 33.38, 34.10, 36.12, 37.60, 113.11, 125.91,
126.80, 127.51, 127.58, 140.73, 142.43, 143.42. Minor
+CDCl3, Me4Si) d 0.87 +s, 3H), 0.92±0.98 +m, 6H), 1.06±
1.69 +m, 8H), 1.80±2.12 +m, 7H), 2.33±2.42 +m, 1H), 4.88
+ddd, Jˆ10.2, 1.5, 1.5 Hz, 1H), 4.96 +ddd, Jˆ17.2, 1.6,
1.6 Hz, 1H), 5.79 +ddd, Jˆ17.1, 10.6, 6.6 Hz, 1H); 13C
NMR +CDCl3, Me4Si) d 13.29, 13.36 +2C), 25.44, 25.51,
28.22, 28.27, 33.55, 34.29, 35.39, 39.07, 39.94, 42.15,
1
isomer: H NMR +CDCl3, Me4Si) d 1.35±1.45 +m, 2H),
1
1.50±1.75 +m, 2H), 1.90±2.25 +m, 5H), 2.40±2.55 +m,
3H), 4.90±5.10 +m, 2H), 5.91 +ddd, Jˆ17.0, 10.3, 6.5 Hz,
1H), 7.20±7.42 +m, 5H); 13C NMR +CDCl3, Me4Si) d 23.54,
29.52, 33.14, 35.03, 36.73, 39.10, 42.82, 112.41, 125.96,
127.51, 127.58, 127.66, 141.00, 143.10, 143.85; HRMS
calcd for C17H20 224.1565, found 224.1565.
111.54, 127.88, 128.55, 144.67. Minor isomer: H NMR
+CDCl3, Me4Si) d 2.19±2.25 +m, 1H), 4.97 +ddd, Jˆ10.6,
1.6, 1.6 Hz, 1H), 5.02 +ddd, Jˆ17.2, 1.8, 1.8 Hz, 1H), 5.90
+ddd, Jˆ17.1, 10.6, 6.1 Hz, 1H), other peaks are covered by
the major isomer; 13C NMR +CDCl3, Me4Si) d 13.27, 13.42
+2C), 25.67, 25.79, 26.90, 27.47, 31.50, 31.54, 32.36, 32.88,
35.88, 35.96, 112.50, 127.48, 128.22, 143.94; HRMS calcd
for C17H28 232.2191, found 232.2186.
4.6.2.
2,3,4,4a,5,6,7,8-Octahydro-1-phenyl-3-ethenyl-
naphthalene ꢀ19d). A 1.2:1 mixture of diasteroisomers,
colorless liquid, GC yield 71%, isolated yield 54%
+130 mg). Major isomer: 1H NMR +CDCl3, Me4Si) d
1.00±1.25 +m, 2H), 1.30±1.80 +m, 6H), 1.85±1.95 +m,
1H), 2.05±2.50 +m, 5H), 4.90±5.11 +m, 2H), 5.88 +ddd,
Jˆ17.2, 10.4, 6.6 Hz, 1H), 7.10±7.42 +m, 5H); 13C NMR
+CDCl3, Me4Si) d 27.01, 28.56, 31.50, 35.22, 35.80, 35.88,
37.56, 37.80, 112.65, 125.88, 127.95, 128.44, 130.42,
4.7.2. 3,4-Diethyl-8-vinylbicyclo[4.4.0]deca-3-ene ꢀ21b).
Column chromatography on silica gel +hexane) afforded
155 mg +36%) of a 2.5:1 mixture of isomers as a colorless
1
liquid, GC yield 41%. Major isomer: H NMR +CDCl3,
Me4Si) d 0.93 +t, Jˆ7.5 Hz, 3H), 0.96 +t, Jˆ7.5 Hz, 3H),
1.11±1.21 +m, 1H), 1.27±1.38 +m, 3H), 1.49±1.81 +m, 6H),
1.86±2.10 +m, 6H), 2.23±2.37 +m, 1H), 4.88 +ddd, Jˆ10.3,
1.5, 1.5 Hz, 1H), 4.96 +ddd, Jˆ17.3, 1.6, 1.6 Hz, 1H), 5.79
+ddd, Jˆ17.1, 10.7, 6.6 Hz, 1H); 13C NMR +CDCl3, Me4Si)
d 13.27, 13.35, 25.66, 25.76, 26.37, 28.54, 30.44, 31.47,
33.03, 34.58, 36.11, 42.15, 111.45, 128.64, 128.82,
1
136.54, 143.38, 143.93. Minor isomer: H NMR +CDCl3,
Me4Si) d 1.00±1.25 +m, 2H), 1.30±1.80 +m, 6H), 1.85±
1.95 +m, 1H), 2.05±2.50 +m, 5H), 4.89±5.10 +m, 2H), 5.83
+ddd, Jˆ17.1, 10.4, 6.5 Hz, 1H), 7.08±7.41 +m, 5H); 13C
NMR +CDCl3, Me4Si) d 26.37, 27.78, 30.48, 35.98, 37.92,
37.98, 38.57, 38.70, 112.30, 125.93, 127.95, 128.49, 128.93,
135.74, 143.69; HRMS calcd for C18H22 238.1721, found
238.1718.
1
144.82. Minor isomer: H NMR +CDCl3, Me4Si) d 0.94 +t,
Jˆ7.5 Hz, 3H), 0.97 +t, Jˆ7.5 Hz, 3H), 4.98 +ddd, Jˆ17.3,
1.7, 1.7 Hz, 1H), other peaks are covered by the major
isomer; 13C NMR +CDCl3, Me4Si) d 13.21, 13.28, 25.68,
25.76, 26.67, 29.71, 32.04, 32.29, 34.50, 35.53, 35.61,
36.88, 111.77, 128.74, 128.81, 144.85; HRMS calcd for
C16H26 218.2035, found 218.2035.
4.6.3. Formation of 2-phenyl-4-methylene-bicyclo[5.3.2]-
dodec-1-ene ꢀ20) by the reaction of zirconacyclopentene
2e with 3-chloro-2-ꢀchloromethyl)propene 5. The reac-
tion procedure and conditions are essentially the same as
those described earlier. Colorless liquid, NMR yield 38%,
4.8. Formation of dienes 22a,b from the CuCl-catalyzed
reaction of zirconacyclopentenes 2 with 3,4-dichloro-
butene 6 at room temperature
1
isolated yield 14% +28 mg). H NMR +CDCl3, Me4Si) d
0.90 +t, Jˆ7.1 Hz, 3H), 1.02±1.45 +m, 7H), 1.60±2.08 +m,
6H), 2.15±2.60 +m, 4H), 2.66 +d, Jˆ14.0 Hz, 1H), 2.86 +d,
Jˆ14.0 Hz, 1H), 4.60 +s, 1H), 4.62 +s, 1H); 13C NMR
+CDCl3, Me4Si) d 14.13, 22.61, 25.18, 30.01, 31.58,
34.46, 35.74, 36.03, 39.34, 41.83, 42.85, 109.06, 130.02,
141.50, 148.41; HRMS calcd for C15H24 204.1878, found
204.1878.
The reaction procedure was essentially the same as that for
the preparation of 19a,b, except that the reaction tempera-
ture was not 508C, but room temperature. The reaction was
stirred at room temperature for 6 h before hydrolysis.
Dienes 22a,b were obtained as pure compounds by column
chromatography on silica gel +hexane).
4.7. Preparation of bicyclic compounds 21a,b from
bicyclic zirconacyclopentanes 3 with 3,4-dichlorobutene
6
4.8.1. 1-Chloro-5,6-diethyl-octa-2ꢀE),5ꢀZ)-diene ꢀ22a).
Colorless liquid, isolated yield 33%. 1H NMR +CDCl3,
Me4Si) d 0.93 +t, Jˆ7.5 Hz, 3H), 0.94 +t, Jˆ7.5 Hz, 3H),
0.97 +t, Jˆ7.5 Hz, 3H), 1.98±2.05 +m, 6H), 2.77 +d,
Jˆ6.1 Hz, 2H), 4.04 +dd, Jˆ7.2, 0.7 Hz, 2H), 5.59 +ddd,
Jˆ15.0, 7.1, 7.1 Hz, 1H), 5.71 +ddd, Jˆ15.1, 6.1, 6.1 Hz,
1H); 13C NMR +CDCl3, Me4Si) d 13.59, 13.61, 13.84, 24.12,
24.30, 24.52, 33.87, 45.56, 125.91, 130.43, 134.88, 138.17;
HRMS calcd for C12H21Cl 200.1332, found 200.1341.
Bicyclic zirconacyclopentanes +2.0 mmol) were prepared in
situ following the reported procedure.26 To the reaction
solution were added 3,4-dichlorobutene +2.0 mmol) and
copper chloride +0.2 mmol). The reaction mixture was
stirred at 508C for 3 h, then was quenched with 3N HCl
and extracted with hexane. The extract was washed with
water and brine, dried over MgSO4. The solvent was
evaporated in vacuo and the residue was puri®ed by column
chromatography on silica gel.
4.8.2. 1-Chloro-5,6-diphenyl-octa-2ꢀE),5ꢀZ)-diene ꢀ22b).
White solid, isolated yield 54%. H NMR +CDCl3, Me4Si)
1
d 1.05 +t, Jˆ7.5 Hz, 3H), 2.65 +q, Jˆ7.5 Hz, 2H), 3.40 +d,
Jˆ6.0 Hz, 2H), 4.07 +d, Jˆ6.8 Hz, 2H), 5.77 +ddd, Jˆ15.2,
6.7, 6.7 Hz, 1H), 5.85 +ddd, Jˆ15.2, 6.0, 6.0 Hz, 1H), 6.99±
7.12 +m, 10H); 13C NMR +CDCl3, Me4Si) d 13.07, 27.59,
37.11, 45.28, 125.73, 125.79, 126.66, 127.48 +2C), 127.50
4.7.1. 3,4-Diethyl-1-methyl-8-vinylbicyclo[4.4.0]deca-3-
ene ꢀ21a). Column chromatography on silica gel +hexane)
afforded 160 mg +35%) of a 2.5:1 mixture of isomers as a

Z. Xi et al. / Tetrahedron 58+2002) 1107±1117
1117
11. Takahashi, T.; Xi, Z.; Yamazaki, A.; Liu, Y.; Nakajima, K.;
Kotora, M. J. Am. Chem. Soc. 1998, 120, 1672.
+2C), 129.64 +4C), 133.09, 133.81, 141.82, 142.55, 142.90;
HRMS calcd for C20H21Cl 296.1332, found 296.1358.
12. Takahashi, T.; Tsai, F. Y.; Li, Y.; Nakajima, K.; Kotora, M.
J. Am. Chem. Soc. 1999, 121, 1119.
Acknowledgements
13. Takahashi, T.; Tsai, F. Y.; Kotora, M. J. Am. Chem. Soc. 2000,
122, 4994.
This work was partially supported by National Science Fund
for Distinguished Young Scholars +29825105), the Major
14. Kotora, M.; Noguchi, Y.; Takahashi, T. Collect. Czech. Chem.
Commun. 1999, 64, 1119.
State
BasicReshearc Development
Program
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Lett. 1986, 27, 2829.
+G2000077502), and National Natural Science Foundation
of China +29702001). Qiu Shi Science and Technologies
Foundation is gratefully acknowledged. This work was
also partially supported by the Ministry of Education,
Science, Sports and Culture, Japan.
16. Takahashi, T.; Kotora, M.; Kasai, K.; Suzuki, N.
Organometallics 1994, 13, 4183.
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