Ruthenium catalyst dichotomy: Selective catalytic diene cycloisomerization or metathesis

Article abstract of DOI:10.1002/1522-2675(20011114)84:11<3335::AID-HLCA3335>3.0.CO;2-4

Ruthenium based catalysts are versatile promoters of a large variety of reactions. A catalytic system active in metathesis has been generated in situ from [RuCl₂(p-cymene)]₂, 1,3-bismesitylimidazolinium chloride, as precursor of a bu

Full text of DOI:10.1002/1522-2675(20011114)84:11<3335::AID-HLCA3335>3.0.CO;2-4

Helvetica Chimica Acta Vol. 84 (2001)
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Ruthenium Catalyst Dichotomy: Selective Catalytic Diene
Cycloisomerization or Metathesis
by David Se¬meril, Christian Bruneau, and Pierre H. Dixneuf*
¬
¬
Institut de Chimie, UMR 6509: Universite de Rennes 1 CNRS, Organometalliques et Catalyse, Campus de
Beaulieu, F-35042 Rennes Cedex
Dedicated to the memory of Professor Luigi M. Venanzi for his innovative contributions to molecular inorganic
chemistry and catalysis
Ruthenium based catalysts are versatile promoters of a large variety of reactions. A catalytic system active
in metathesis has been generated in situ from [RuCl2(p-cymene)]2, 1,3-bismesitylimidazolinium chloride, as
precursor of a bulky carbene ligand, and cesium carbonate. We report that this three component catalytic system
exhibits dichotomous reactivity for the transformation of dienes, providingan active catalytic system for the
cycloisomerization of dienes to methylidene five-membered cyclic molecules, whereas, in the presence of
acetylene, a metathesis catalyst is generated that transforms the same dienes into cyclic olefins with loss of
ethylene.
Introduction. Duringthe last decade, ruthenium-based catalysts have shown their
versatility as promoters of a large variety of innovative combinations of molecules that
are very useful for fine chemistry [1]. The development of efficient Ru catalysts
depends not only on their ease of preparation, but also on the ability of a single catalytic
system to provide a broad range of selective reactions. New trends especially focus on
the search for unique modifications of a catalytic system in situ that completely modify
the transformation of a substrate to provide two selective transformations of the same
substrate catalyzed by a single initial metal complex. Among Ru-catalyzed reactions,
alkene metathesis has recently become a powerful tool in many branches of organic
synthesis [2], supramolecular and organometallic chemistry [3], and polymers [4] due
to the discovery of well-defined active Ru catalysts that are tolerant of a variety of
functional groups [5]. This motivates sustained efforts to create new alkene metathesis
catalysts by improvingcatalyst efficiency and through discovery of −tunable× catalysts
that exhibit multifaceted reactivity.
Recently, a new catalytic system active for metathesis has been generated in situ
from [RuCl2(p-cymene)]2, 1,3-bismesitylimidazolinium chloride as precursor of a
bulky carbene ligand, and Cs2CO3. The resultingsystem (catalyst A), which is very
efficient for the ring-closing metathesis of enynes, produced six-membered siloxanes
featuringa conjugated 1,3-diene structure ( Scheme 1) [6].
We now report that the same three-component catalytic system A exhibits two
reactivities for the transformation of dienes. It provides an active catalytic system for
the cycloisomerization of dienes 1 to methylene five-membered cyclic ylidenes 2,
whereas, in the presence of C2H2, it generates a metathesis catalyst that transforms the
same dienes 1 into cyclic olefins 3 with loss of C2H4 (Scheme 2).

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Helvetica Chimica Acta Vol. 84 (2001)
Scheme 1
Scheme 2
Results and Discussion. The catalyst system A, in an attempt to generate in situ a
RuCl2(carbene)(arene) complex accordingto the reaction of less sterically hindered
imidazolinylidene carbenes [7], was simply prepared by the addition to 2.5 mol-% of
[RuCl2(p-cymene)]2 of 5 mol-% of 1,3-bismesitylimidazolinium chloride and 10 mol-%
of Cs2CO3 in 2.5 ml of toluene under N2. Then 0.5 mmol of diallyltosylamide 1a was
immediately added to the stirred solution and was completely converted after 1 h of
reaction at 808 exclusively to 2a, which was isolated in 88% yield (Scheme 3). Using1,3-
bismesitylimidazolium chloride in the catalytic system leads to a less-electron-rich
carbene ligand, and gave a slower and less-selective reaction. The complete conversion
of 1a required 16 h of reaction at 808 and produced a 3 :1 mixture of 2a and 4a,
resultingfrom the isomerization of one allyl branch to a prop-1-en-1-yl group. A fast
reaction, completed within 2 h at 808, was also observed when 1,3-bis(2,6-diisopropyl-
phenyl)imidazolinium chloride was used as the carbene precursor, but the catalytic
system was somewhat less selective than A (2a and 4a were formed in the ratio 2.3 :1).
These initial observations clearly show that the activity and selectivity of the
catalyst generated in situ strongly depend on the nature of the imidazolium or
Scheme 3

Helvetica Chimica Acta Vol. 84 (2001)
3337
imidazolinium salt and that the 1,3-bismesitylimidazolinium chloride leads to the most
efficient catalyst for cycloisomerization.
By contrast, when the transformation of the diene 1a was performed with catalyst A
under an atmosphere of C2H2 instead an inert gas (N2 or Ar), it was completely
converted after 2.5 h of reaction at 808 exclusively to the metathesis compound 3a.
Thus, the presence of C2H2 completely changed the course of the reaction: no
cycloisomerization product 2a was detected, suggesting that the catalytic species giving
rise to this product was no longer present. The influence of other alkynes was tested,
and we found that the addition of 4.8 equiv. of 1-hexyne also led to the complete
formation of the metathesis compound 3a after 4 h at 808. On the other hand, the
presence of the more bulky (tert-butyl)acetylene gave a poor conversion and favored
the formation of 2a and 4a in the ratio 4 :1, whereas trimethylsilylacetylene promoted
good conversion, but without selectivity, with compounds 2a, 3a, and 4a produced in the
ratio 3 :12 :5, respectively. Amongthe aromatic alkynes, only phenylacetylene was able
to induce the metathesis reaction, albeit with concomitant formation of the cyclo-
isomerization product 2a in 10% yield. Consequently, because of its efficiency and
facile elimination at the end of the reaction, C2H2 appeared to be the additive of choice
for reversal of selectivity of the initial catalyst system A towards the formation of the
metathesis compound.
The activity and selectivity of the catalytic system A under two types of conditions
was used for the transformation of other functional 1,6-dienes. Thus, under N2, catalyst
A completely transformed the dienes 1b d (0.5 mmol in toluene) to the methylene-
cyclopentanes 2b d, which were isolated in 64, 85, and 78% yields, respectively, after
8 h at 808 (Scheme 4).
By contrast, with catalyst A under C2H2, the same dienes 1b 1d were completely
and selectively converted to the cyclopentene derivatives 3b d, which were isolated in
72, 68, and 82% yields, respectively. The catalytic system for the metathesis reaction
Scheme 4

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Helvetica Chimica Acta Vol. 84 (2001)
generated in situ under C2H2 completely inhibited cycloisomerization, but was slightly
less efficient than cycloisomerization catalyst A, requiring8 ( 3b) or 16 h (3c,d) for the
reaction to go to completion.
It is noteworthy that Kurosawa [8] recently reported a catalytic system based on the
ionic Ru precursor [RuCl(PCy3)(PhCH2CH2OH)][BF4], which converted a diene to
its RCM reaction product in the presence of 5 mol-% of phenylacetylene. Our catalytic
system based on a diaminocarbene Ru system appears to be significantly more reactive.
The high selectivity of the reactions described indicates that the presence of C2H2
rapidly generates from catalyst A a species that catalyzes metathesis and prevents the
formation of the species that catalyzes cycloisomerization. This is likely due to a strong
interaction of the alkyne with the Ru center, even in the presence of diene, which might
generate a h1-vinylidene-Ru intermediate [9]. In both cases, the imidazolinium salt in
the presence of the base Cs2CO3 is likely to generate the aminocarbene ligand, which is
expected to react with [RuCl2(p-cymene)]2 to form the RuX2(imidazolinylidene)(p-
cymene) complex as observed from isolated imidazolylidene carbenes [7][10].
However, we have shown for metathesis of enynes that the resultingcatalyst of type
A with aromatic imidazolylidene carbene [11] is more active than the isolated
RuCl2(imidazolylidene)(p-cymene) complex, and we can suggest that the decoordi-
nation of p-cymene readily occurs, generating a highly coordinatively unsaturated
species of type [RuX2(imidazolinylidene)], stabilized by the bulkyness of the carbene
ligand, which might be the catalyst species B. Consequently, the cycloisomerization
reaction can be explained accordingto Scheme 5. The RuII catalytic species B may
coordinate the diene and give the oxidative addition product C. Indeed, the oxidative
Scheme 5

Helvetica Chimica Acta Vol. 84 (2001)
3339
addition process is expected to be favored at a RuII site by an electron-donating
ancillary ligand, and it is well-known that imidazolinylidene ligands are particularly
electron-releasing[12]. b-Elimination within C should lead to the hydrido-RuIV
intermediate D, which would give the cycloisomerization product 2 by reductive
elimination.
By contrast, in the presence of C2H2 and diene 1, the catalytic species of type B may
lead preferentially to the vinylidene species E (Scheme 6). Indeed, in the presence of a
terminal alkyne, the easy formation of vinylidene-Ru species from [RuCl2(p-cymene)]2
and electron donor ligands is well-documented, and the resulting vinylidene-metal
complexes are known to be active in alkene metathesis for ROMP polymerization [13].
Thus, the vinylidene-Ru species E is expected to interact with one CˆC bond of the
diene to lead to the carbene F and, via oxidative coupling, to the metallacyclobutane G.
Intermediate G is the precursor of the metathesis product 3 and the reactive carbene H,
which is expected to give again the carbene F via intermediate I.
Scheme 6
Conclusions. The above observations show, in addition to the metathesis of
enynes, two new catalytic faces of the three-component catalyst A generated in the
presence of a variety of functional dienes. The behavior of catalyst A is dichotomous: in
the presence of a diene 1, it spontaneously gives the cycloisomerization product 2,
whereas, with C2H2, this reaction is inhibited and the activity of catalyst A is reoriented
toward exclusive formation of the RCM metathesis product. Thus, C2H2 can tune the
activity of catalytic system A and force it to deviate from its standard catalytic role to
function in a new way.
¬
The authors are grateful to CNRS, MRT, Region Bretagne, and the E. U. COST Programme (Action D12/
0025/99) for financial support.

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Helvetica Chimica Acta Vol. 84 (2001)
Experimental Part
General. 1H-NMR Spectra: in CDCl3 at 200 MHz; 13C-NMR spectra in CDCl3 at 50 MHz, unless otherwise
noted; chemical shifts d in ppm, couplingconstants J in Hz. GC-MS: m/z (rel. %).
General Procedure for the Catalytic Cycloisomerization Reaction. Into a Schlenk tube under Ar were
introduced 7.6 mg(0.0125 mmol, 2.5 mol %) [RuCl 2(p-cymene)]2, 10.4 mg(0.025 mmol, 5 mol %) 1,3-
dimesitylimidazolinium chloride, 16.3 mg(0.05 mmol, 10 mol %) Cs 2CO3, and 0.5 mmol of diene, and 2.5 ml of
degassed toluene was added. The mixture was heated to 808 until the reaction was complete (duration
dependingon the nature of the diene), and, after coolingto r.t., the toluene was evaporated under reduced
pressure. The crude product was purified by flash chromatography (FC) on silica gel (Et2O/pentane).
General Procedure for the Catalytic Alkene Metathesis Reaction in the Presence of C2H2. The reagents were
introduced into a Schlenk tube under Ar as described above. After adding2.5 ml degassed toluene, the Schlenk
tube was purged 3 Â with C2H2 (1 atm) before heatingat 80 8 until the reaction was complete (duration
dependingon the nature of the diene). After coolingto r.t., the toluene was evaporated under reduced pressure.
The crude product was purified by FC on silica gel (Et2O/pentane).
3-Methyl-4-methylidene-1-(toluene-4-sulfonyl)pyrrolidine (2a). 1H-NMR: 1.01 (d, 3J ˆ 6.3, CHMe); 2.41
(s, MePh); 2.66 (m, NCH2CH); 3.35 3.65 (m, CHMe); 3.71 (dm, 2J ˆ 14.1, 1 H, CH2CˆCH2); 3.93 (dm, 2J ˆ
14.1, 1 H, CH2CˆCH2); 4.88 (dm, 2J ˆ 1.6, 1 H, CˆCH2); 4.93 (dm, 2J ˆ 1.6, 1 H, CˆCH2); 7.30 (d, 3J ˆ 8.1,
2 arom. H); 7.68 (d, 3J ˆ 8.1, 2 arom. H). 13C-NMR: 16.1 (CHMe); 21.6 (MePh); 37.5 (CHMe); 52.2, 55.1
(NCH2); 106.1 (CˆCH2); 127.8, 129.7 (arom. CH); 137.1 (ipso-SO2 C); 143.7 (ipso-Me); 149.3 (CˆCH2). GC-
‡
MS: 251 (18, [M] ), 236 (9), 155 (26), 97 (8), 96 (90), 95 (9), 94 (19), 92 (16), 91 (97), 90 (5), 89 (11), 81 (14),
80 (25), 76 (9), 77 (8), 70 (7), 69 (100), 68 (40), 67 (47), 66 (8), 67 (79), 64 (6), 63 (15), 56 (6), 55 (12), 54 (8), 53
(21), 52 (5), 55 (11), 50 (5), 42 (39), 41 (98), 40 (12), 39 (47), 32 (5), 30 (9), 29 (6), 28 (12), 27 (16).
2,8,8-Trimethyl-3-methylidene-7,9-dioxaspiro[4.5]decane (2b). 1H-NMR: 1.04 (d, 3J ˆ 6.7, CHMe); 1.34
(s, CMe2); 1.68 (d, 2J ˆ 5.6, 1 H, CCH2C); 1.97 (dd, 2J ˆ 12.8, 3J ˆ 5.6, 1 H, CCH2CH); 2.11 2.39 (m, 2 H,
CCH2C, CCH2CH); 2.39 2.60 (m, CHMe); 3.59 (s, 2OCH2); 4.71 4.79 (m, 1 H, CˆCH2); 4.79 4.99 (m, 1 H,
CˆCH2). 13C-NMR: 18.7 (CHMe); 23.4, 24.4 (CMe2); 36.4 (CHMe); 39.6 (CMe2); 40.6 (CCH2CH); 41.43
(CCH2CˆCH2); 68.4, 69.6 (2 OCH2); 97.8 (C(CH2)4); 105.4 (CˆCH2); 155.3 (CˆCH2). GC-MS: 196 (<1,
‡
[M] ), 182 (12), 181 (73), 120 (38), 107 (10), 104 (5), 93 (9), 92 (28), 90 (9), 79 (5), 76 (6), 59 (5), 55 (7), 53
(10), 51 (5), 44 (5), 43 (100), 42 (12), 41 (39), 40 (11), 39 (33), 32 (12), 31 (6), 29 (17), 28 (53), 27 (14).
1-Ethoxy-3-methyl-4-methylidene-1-phenylcyclopentane (2c). Two diastereoisomers (57:43). Major dia-
3
stereoisomer: 1H-NMR: 1.11 (d, 3J ˆ 6.9, CHMe); 1.21 (t, 3J ˆ 7.0, OCH2Me); 1.65 (dd, 2J ˆ 12.9, J ˆ 11.5, 1 H,
CCH2CH); 1.90 2.70 (m, 3 H, CCH2C, CCH2CH); 2.70 3.08 (m, CHMe); 3.15 (q, J ˆ 7.0, OCH2Me); 4.85
4.95 (m, 1 H, CˆCH2); 4.95 5.07 (m, 1 H, CˆCH2); 7.11 7.50 (m, 5 arom. H). 13C-NMR: 16.0 (OCH2Me);
18.8 (CHMe); 36.4 (CHMe); 44.6 (CCH2CH); 45.0 (CCH2CˆCH2); 58.9 (OCH2Me); 85.2 (COCH2Me); 105.5
(CˆCH2); 125.7, 126.5, 126.8, 128.2, 136.2 (arom. C); 143.5 (ipso C); 155.6 (CˆCH2). Minor diastereoisomer:
1H-NMR: 1.08 (d, 3J ˆ 6.9, CHMe); 1.22 (t, 3J ˆ 7.0, OCH2Me); 1.90 2.70 (m, 4 H, CCH2C, CCH2CH); 2.70
3.08 (m, CHMe); 3.32 (q, 3J ˆ 7.0, OCH2Me); 5.98 6.06 (m, 1 H, CˆCH2); 6.15 6.23 (m, 1 H, CˆCH2); 7.11
7.50 ( m, 5 arom. H). 13C-NMR: 15.9 (OCH2Me); 20.0 (CHMe); 35.9 (CHMe); 44.8 (CCH2CH); 47.3
(CCH2CˆCH2); 59.2 (OCH2Me); 85.0 (COCH2Me); 105.7 (CˆCH2); 126.1, 126.4, 127.2, 128.3, 133.5 (arom.
‡
C); 144.3 (ipso C); 155.4 (CˆCH2). GC-MS (of the diastereoisomer mixture): 216 (11, [M] ), 215 (8), 201 (13),
187 (8), 175 (5), 174 (7), 173 (21), 172 (7), 171 (31), 170 (100), 169 (7), 157 (11), 156 (9), 155 (47), 154 (7), 153
(9), 152 (6), 147 (6), 146 (5), 145 (30), 143 (30), 142 (6), 141 (11), 129 (6), 128 (27), 127 (19), 126 (8), 116 (7),
114 (13), 105 (8), 104 (37), 91 (6), 90 (8), 77 (13), 76 (12), 67 (6), 55 (13), 53 (13), 52 (7), 51 (26), 50 (7), 45 (6),
43 (33), 42 (7), 41 (37), 40 (12), 39 (33), 32 (7), 31 (8), 29 (46), 28 (27), 27 (26).
1-Butyl-1-ethoxy-3-methyl-4-methylidenecyclopentane (2d). Two diastereoisomers (55 :45). Major diaster-
1
eoisomer: H-NMR: 0.89 (t, 3J ˆ 6.8, CH2CH2Me); 1.10 (d, 3J ˆ 6.7, CHMe); 1.11 (t, 3J ˆ 7.0, OCH2Me); 1.19
1.32 (m, CH2CH2Me); 1.32 1.46 (m, CCH2CH2); 1.82 2.15 (m, CCH2CH); 2.22 (d, 2J ˆ 27.6, CCH2CˆCH2);
2.28 2.65 (m, CHMe); 3.57 (q, 3J ˆ 7.0, OCH2Me); 4.75 (d, 2J ˆ 2.2, 1 H, CˆCH2); 4.82 (d, 2J ˆ 2.2, 1 H,
CˆCH2). 13C-NMR: 14.2 (CH2CH2Me); 16.0 (OCH2Me); 18.4 (CHMe); 23.2 (CH2CH2Me); 26.4 (CH2CH2Me);
35.9 (CCH2CH2); 36.4 (CHMe); 43.9 (CCH2CH); 44.8 (CCH2CˆCH2); 56.7 (OCH2); 83.7 (COCH2Me); 104.6
(CˆCH2); 156.4 (CˆCH2). Minor diastereoisomer: 1H-NMR: 0.89 (t, 3J ˆ 6.8, CH2CH2Me); 1.10 (d, 3J ˆ 6.7,
CHMe); 1.15 (t, 3J ˆ 7.0, OCH2Me); 1.19 1.32 (m, CH2CH2Me); 1.32 1.46 (m, CCH2CH2); 1.82 2.15
(m, CCH2CH); 2.22 (d, 2J ˆ 27.6, CCH2CˆCH2); 2.28 2.65 (m, CHMe); 3.61 (q, 3J ˆ 7.0, OCH2Me); 4.74
(d, 2J ˆ 2.2, 1 H, CˆCH2); 4.86 (d, 2J ˆ 2.2, 1 H, CˆCH2). 13C-NMR: 14.2 (CH2CH2Me); 16.1 (OCH2Me); 20.1
(CHMe), 23.2 (CH2CH2Me); 25.8 (CH2CH2Me); 35.3 (CCH2CH2); 36.4 (CHMe); 44.5 (CCH2CH); 44.6 (CCH2

Helvetica Chimica Acta Vol. 84 (2001)
3341
CˆCH2); 57.4 (OCH2); 83.4 (COCH2Me); 105.3 (CˆCH2); 155.8 (CˆCH2). GC-MS (of the diastereoisomer
‡
mixture): 196 (21, [M] ), 181 (6), 168 (8), 167 (53), 154 (7), 153 (11), 151 (5), 150 (17), 139 (17), 138 (99), 127
(11), 126 (5), 125 (6), 124 (15), 120 (15), 120 (12), 111 (10), 110 (56), 108 (8), 107 (10), 106 (11), 98 (10), 96
(10), 95 (5), 94 (16), 93 (10), 92 (12), 90 (12), 85 (7), 84 (7), 82 (11), 81 (5), 80 (10), 78 (12), 76 (11), 68 (14), 67
(11), 57 (35), 56 (13), 55 (39), 54 (16), 53 (15), 52 (6), 45 (7), 44 (5), 43 (76), 42 (19), 41 (100), 40 (17), 39 (34),
31 (5), 29 (82), 28 (18), 27 (35).
1-(Toluene-4-sulfonyl)-2,5-dihydropyrrole (3a). 1H-NMR: 2.40 (s, MePh); 4.10 (s, 2 NCH2); 5.63
(s, CHˆCH); 7.30 (d, 3J ˆ 8.6, 2 arom. H); 7.70 (d, 3J ˆ 8.6, 2 arom. H). 13C-NMR (50.329 MHz): 21.6 (Me);
54.9 (2 NCH2); 125.5 (CHˆCH); 127.5, 129.8 (arom. C); 134.3 (ipso-SO2 C); 143.5 (ipso-Me). GC-MS: 223 (28,
‡
[M] ), 155 (28), 91 (72), 68 (100), 41 (19).
8,8-Dimethyl-7,9-dioxaspiro[4.5]dec-2-ene (3b). 1H-NMR: 1.40 (s, CMe2); 2.21 (s, 2 CCH2O); 3.64
(s, 2 CH2CH); 5.58 (s, CHˆCH). 13C-NMR: 23.9 (CMe2); 40.2 (2 CCH2CH); 40.8 (C(CH2CH)2); 69.3
‡
(C(OCH2)2); 97.7 (CMe2); 128.7 (CHˆCH). GC-MS: 168 (<1, [M] ), 154 (7), 153 (48), 93 (37), 91 (11), 81
(6), 80 (36), 79 (38), 78 (6), 77 (19), 59 (14), 53 (6), 43 (33), 41 (6), 39 (10), 32 (23), 29 (6), 28 (100), 27 (5).
4-Ethoxy-4-phenylcyclopentene (3c). 1H-NMR: 1.15 (t, 3J ˆ 7.0, OCH2Me); 2.73 (d, 2J ˆ 15.5, 2 H,
C(CH2)2); 2.89 (d, 2J ˆ 15.5, 2 H, C(CH2)2); 3.20 (q, 3J ˆ 7.0, OCH2Me), 5.76 (s, 2 H, CHˆCH); 7.10 7.46
(m, 5 arom. H). 13C-NMR: 15.9 (OCH2Me); 40.1 (2 CH2CH); 59.2 (OCH2Me); 87.6 (COCH2Me); 125.4, 128.2,
‡
128.4 (arom. C); 128.6 (CHˆCH); 145.8 (ipso C). GC-MS: 188 (100, [M] ), 187 (25), 160 (5), 159 (22), 145
(11), 144 (8), 143 (31), 142 (34), 141 (31), 130 (11), 128 (20), 127 (22), 126 (5), 116 (9), 115 (8), 114 (28), 105
(14), 104 (89), 90 (7), 77 (11), 76 (27), 55 (5), 54 (5), 53 (7), 52 (5), 51 (19), 50 (8), 43 (10), 41 (5), 39 (26), 31
(9), 29 (34), 28 (31), 27 (26).
4-Butyl-4-ethoxycyclopentene (3d). 1H-NMR: 0.88 (t, 3J ˆ 7.0, CH2CH2Me); 1.13 (t, 3J ˆ 7.0, OCH2Me);
1.20 1.36 (m, CH2CH2Me); 2.26 (d, 2J ˆ 15.6, 2 H, C(CH2)2); 2.46 (d, 2J ˆ 15.6, 2 H, C(CH2)2); 3.29 (q, 3J ˆ 7.0,
OCH2Me); 5.60 (s, CHˆCH). 13C-NMR: 14.2 (CH2CH2Me); 16.1 (OCH2Me); 23.3 (CH2CH2Me); 26.3
(CH2CH2Me); 38.6 (CCH2CH2); 43.2 (C(CH2)2); 57.5 (OCH2Me); 85.5 (COCH2Me); 128.7 (CHˆCH). GC-
‡
MS: 168 (15, [M] ), 138 (13), 125 (10), 124 (6), 111 (17), 110 (85), 97 (9), 85 (6), 84 (15), 83 (14), 82 (39), 81
(5), 80 (6), 79 (7), 78 (9), 77 (5), 76 (7), 67 (8), 66 (9), 65 (6), 58 (7), 57 (84), 56 (17), 55 (57), 54 (24), 53 (20),
52 (7), 51 (8), 45 (5), 53 (42), 42 (13), 41 (86), 40 (12), 39 (49), 31 (8), 30 (6), 29 (100), 28 (27), 27 (53), 26 (5).
REFERENCES
[1] a) T. Naota, H. Takaya, S. I. Murahashi, Chem. Rev. 1998, 98, 2599; b) B. M. Trost, F. D. Toste, A. B.
Pinkerton, Chem. Rev. 2001, 101, 2067; c) C. Bruneau, P. H. Dixneuf, Chem. Commun. 1997, 507.
[2] a) M. Schuster, S. Blechert, Angew. Chem., Int. Ed. 1997, 36, 2036; b) T. M. Trnka, R. H. Grubbs, Acc.
Chem. Res. 2001, 34, 18.
[3] C. Dietrich-Buchecker, G. Rapenne, J. P. Sauvage, Coord. Chem. Rev. 1999, 185 186, 167.
[4] a) K. J. Ivin, J. Mol. Catal., A: Chem. 1998, 131, 1; b) K. J. Ivin, J. C. Mol, −Olefin Metathesis
Polymerisation×, Academic Press, New York, 1997.
[5] a) A. F¸rstner, Top. Catal. 1997, 4, 285; b) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413.
¬
¬
[6] D. Semeril, M. Cleran, C. Bruneau, P. H. Dixneuf, Adv. Synth. Catal. 2001, 343, 184.
[7] a) B. fietinkaya, I. ÷zdemir, P. H. Dixneuf, J. Organomet. Chem. 1997, 534, 153; b) B. fietinkaya, I.
÷zdemir, C. Bruneau, P. H. Dixneuf, J. Mol. Catal., A: Chem. 1997, 118, L1 L4; c) H. K¸cÀ¸kbay, B.
fietinkaya, S. Guesmi, P. H. Dixneuf, Organometallics 1996, 15, 2434.
[8] Y. Miyaki, T. Onishi, S. Ogoshi, H. Kurosawa, J. Organomet. Chem. 2000, 616, 135.
[9] C. Bruneau, P. H. Dixneuf, Acc. Chem. Res. 1999, 32, 311.
[10] a) L. Jafarpour, S. P. Nolan, J. Organomet. Chem. 2001, 617 618, 17; b) J. Louie, R. H. Grubbs, Angew.
Chem., Int. Ed. 2001, 40, 247.
[11] L. Ackermann, C. Bruneau, P. H. Dixneuf, Synlett 2001, 397.
[12] a) D. J. Cardin, B. fietinkaya, M. F. Lappert, Chem. Rev. 1972, 72, 545; b) B. fietinkaya, P. H. Dixneuf, M. F.
Lappert, J. Chem. Soc., Dalton Trans. 1974, 1827.
[13] a) H. Katayama, H. Urushima, F. Ozawa, J. Organomet. Chem. 2000, 606, 16; b) H. Katayama, U.
Urushima, F. Ozawa, Chem. Lett. 1999, 369; c) H. Katayama, F. Ozawa, Organometallics 1998, 17, 5190;
d) H. Katayama, F. Ozawa, Chem. Lett. 1998, 67.
Received August 29, 2001