Highly selective dimerization of styrenes and linear co-dimerization of styrenes with ethylene catalyzed by a ruthenium complex

Article abstract of DOI:10.1002/anie.200701583

(Chemical Equation Presented) Heads you win: An unusual head-to-head dimerization of styrenes has been developed using the zero-valent ruthenium catalyst [Ru(η⁶-cot)(η²-dmfm)₂] (cot = 1,3,5-cyclooctatriene, dmfm = dimethyl fumarate) in the presence of primary alcohols to give the homo-dimer in high regio- and stereoselectivity. The catalyst system is also effective for the selective co-dimerization of styrenes with ethylene to give the co-dimer in high yield.

Full text of DOI:10.1002/anie.200701583

Communications
DOI: 10.1002/anie.200701583
Homogeneous Catalysis
Highly Selective Dimerization of Styrenes and Linear Co-dimerization
of Styrenes with Ethylene Catalyzed by a Ruthenium Complex**
Teruyuki Kondo,* Daisuke Takagi, Hiroshi Tsujita, Yasuyuki Ura, Kenji Wada, and
Take-aki Mitsudo
In memory of Yoshihiko Ito
The homo- and co-dimerization of alkenes are important
methods for generating higher alkenes, which are a source of
new kinds of polymers, lubricants, detergents, and many other
useful chemicals.[1] Considerable attention has recently been
focused on these reactions, because of the demand for atom-
efficient organic syntheses, that is, all of the atoms in the
starting materials are incorporated into the products (100%
atom economy).[2]
The first transition-metal complexes that were shown to
catalyze the homo-dimerization of styrenes were based on
palladium.[3] Later, nickel-[4] and zirconium-based[5] catalyst
systems were shown to be effective for this dimerization
reaction, and these generally gave head-to-tail dimers, namely
(E)-1,3-diaryl-1-butenes. There has been only one previous
example of head-to-head dimerization to give (E)-1,4-diaryl-
1-butene: Kretschmer et al.[6] reported that the use of a
bis(indenyl)yttrium hydride as the catalyst gave such a
dimerization. However, their catalyst is unstable towards air
and moisture.
The co-dimerization of styrenes with ethylene has also
been extensively studied since it was first reported in 1965.[7]
Many transition-metal complexes are active in this process,[8,9]
and catalysts containing nickel are the most active.[10,11] The
products are head-to-tail dimers (3-aryl-1-butenes), and an
enantioselective version of the co-dimerization (hydroviny-
lation) of styrenes with ethylene has recently been devel-
oped.[11,12]
In the course of our study on the synthesis and catalytic
activity of low-valent ruthenium complexes[13] as well as
ruthenium-catalyzed co-dimerization reactions of different
alkenes,[14] we found that the zero-valent ruthenium complex
[Ru(h6-cot)(h2-dmfm)2][15]
(cot = 1,3,5-cyclooctatriene,
dmfm = dimethyl fumarate) in the presence of primary
alcohols efficiently catalyzes an unusual head-to-head dime-
rization of styrenes to give (E)-1,4-diaryl-1-butenes.[16,17] This
catalyst system is also effective for the selective linear co-
dimerization of styrenes with ethylene to give (E)-1-aryl-1-
butenes in good yields and high selectivity.
The catalytic activity of several ruthenium complexes was
initially examined in the dimerization of styrene (1a) to give
the head-to-head dimer 2a [Eq. (1)].
Of the complexes examined, [Ru(h6-cot)(h2-dmfm)2]
showed the highest catalytic activity, and 2a was obtained in
67% yield with high E selectivity (95%). [Ru(h4-cod)(h6-
cot)] (cod = 1,5-cyclooctadiene) and [Ru(h5-C8H11)(h5-
C6H5O)]·PhOH[18] also showed moderate catalytic activity to
give 2a in respective yields of 36% and 25% (E isomer,
95%), while no reaction occurred with divalent ruthenium
complexes, such as [{RuCl2(CO)3}2], [RuCl2(h4-cod)]n,
[{RuCl2(p-cymene)}2], [RuH2(PPh3)4], [RuHCl(CO)(PPh3)3],
{RuCl2(PPh3)3)], and [Cp*RuCl(h4-cod)] (Cp* = penta-
methylcyclopentadienyl).
The effect of the solvent in the presence of 1-propanol was
then examined. In the present reaction, mesitylene proved to
be the best solvent, and 2a was obtained in 67% yield. The
reaction also proceeded in toluene (2a, 51%), 1,4-dioxane
(2a, 50%), and diglyme (2a, 33%). In contrast, 2a was not
obtained in N,N-dimethylformamide (DMF) or dimethyl
sulfoxide (DMSO) because of their strong ability to co-
ordinate to an active ruthenium species. The concomitant use
of primary alcohols is essential for the success
of the present reaction (see below); however, when 1-
propanol was used as the solvent without mesitylene, the
yield of 2a decreased to 57%.
[*] Prof. Dr. T. Kondo, D. Takagi, Dr. H. Tsujita, Dr. Y. Ura, Dr. K. Wada,
Prof. Dr. T. Mitsudo
Department of Energy and Hydrocarbon Chemistry
Graduate School of Engineering
Kyoto University
Nishikyo-ku, Kyoto 615-8510 (Japan)
Fax: (+81)75-383-2805
E-mail: teruyuki@scl.kyoto-u.ac.jp
[**] This work was supported in part by Grants-in-Aid for Scientific
Research (B), Scientific Research on Priority Areas, “Advanced
Molecular Transformations of Carbon Resources” from the Japan
Society for the Promotion of Science and the Ministry of Education,
Culture, Sports, Science, and Technology, Japan. This research was
conducted in part at the Advanced Research Institute of Environ-
mental Material Control Engineering, Katsura-Int’tech Center,
Graduate School of Engineering, Kyoto University.
The type and the amount of alcohols used are critical for
the success of the present catalytic reaction. No reaction
occurred without the presence of primary alcohols, such as
ethanol, 1-propanol, and 1-octanol. Secondary and tertiary
alcohols were not suitable for this reaction. Three equivalents
(6.0mmol), relative to styrene ( 1a)), of low-boiling-point
5958
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Angew. Chem. Int. Ed. 2007, 46, 5958 –5961

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Chemie
primary alcohols, such as ethanol and 1-propanol, were
required to give 2a (64% for ethanol and 67% for
1-propanol). In sharp contrast, when three equivalents of
1-octanol were used, the reaction became sluggish, and
undesirable by-products, such as 1-octanal and octyl octan-
oate, as well as a considerable amount of ethylbenzene
derived from the hydrogenation of styrene (1a), were
produced (2a, 19%). To suppress the formation of these by-
products, the amount of 1-octanol was reduced from 6.0mmol
to 0.50 mmol and the reaction was carried out at a lower
reaction temperature (808C) to give 2a in the highest yield of
80% with high E selectivity (95%).
To elucidate the mechanism of this reaction a deuterium-
labeling experiment using [D1]ethanol was performed for the
dimerization of styrene (1a) to give 2a. The reaction gave a
mixture of mono-deuterio-(E)-1,4-diphenyl-1-butenes ([D1]-
2a, m/z = 209 [M+]), predominantly, and almost no [D2]-2a
(m/z = 210[ M+]) or [D3]-2a (m/z = 211 [M+]) was obtained.
An NMR study showed that a deuterium atom was distrib-
uted at four positions in [D1]-2a [Eq. (3)].
Under the optimum reaction conditions, the correspond-
ing head-to-head dimers (2a–d) were obtained from styrene
derivatives 1a–d in good to high yields with high regio- and
stereoselectivity [Eq. (2); figures in the parentheses give yield
This deuterium scrambling suggests the formation of a
ruthenium hydride ([Ru]-H) species as well as a ruthenium
deuteride ([Ru]-D) species, which promote the rapid H/D
exchange of the starting styrene (1a) to [D1]-1a through an
addition/b-hydrogen elimination mechanism. When isolated
2a and [D1]-2a were respectively treated with [D1]ethanol
under the same reaction conditions, neither deuterium
incorporation into 2a nor a change in the deuterium
distribution of [D1]-2a was observed. This result strongly
suggests that deuterium exchange occurs with the starting
styrene (1a), and not with the formed 2a. This proposal can
also explain why the present reaction gave only dimers and
not trimers or oligomers.
of isolated product]. As described above, 1-octanol
(0.50 mmol) was most effective for styrene derivatives 1a,
1b, and 1d, while 1-propanol (6.0mmol) was suitable for 1c
when the reaction was performed at 1108C. When the
reaction of 1c was carried out in the presence of 1-octanol
instead of 1-propanol at 808C, the yield of 2c decreased from
66% to 40%. No significant effect was observed for
substituents on the phenyl ring of the styrene derivatives.
The time-course of the dimerization of 1a to 2a is shown
in Figure 1, which clearly indicates the presence of an
induction period. This finding suggests that a catalytically
Although the reaction mechanism is not yet clear, three
possible mechanisms are illustrated in Scheme 1. In path A,
2
À
the oxidative addition of an sp C H bond in styrene (1a) to a
Ru0 species proceeds to give a (hydrido)(alkenyl)ruthenium
À
intermediate. Subsequent insertion of 1a into either a [Ru] H
À
bond or an alkenyl [Ru] bond, followed by reductive
elimination would give dimer 2a. In path B, a [Ru]-H species
is first generated by the oxidative addition of primary alcohols
to a Ru0 species. Successive double insertion of 1a and
stereoselective b-hydrogen elimination give the correspond-
ing dimer 2a with regeneration of a [Ru]-H species. Path C
involves the oxidative cyclization of two molecules of 1a onto
a Ru0 species to give a ruthenacyclopentane intermediate.[19]
The ring-opening of a ruthenacyclopentane by the primary
alcohol, followed by a stereoselective b-hydrogen elimination
would give dimer 2a. If path B is operative, an initial 1,2-
À
insertion of styrene (1a) into a [Ru] H bond should be
considered despite the well-known electronic preference of
styrenes for 2,1-insertion,[20] even in the case of a ruthenium
species. Therefore, we suggest that the present reaction might
occur according to path C. The ring-opening of a ruthena-
cyclopentane by the direct b-hydrogen elimination is not a
favored process, but this could be facilitated by protonation or
s-bond metathesis[21] with the primary alcohol, which plays
the role of co-catalyst. Then, the stereoselective b-hydrogen
elimination could occur to give dimer 2a with regeneration of
the Ru0 species and the primary alcohol co-catalyst.
Figure 1. The time-course of the dimerization of 1a to 2a.
active species is formed from [Ru(h6-cot)(h2-dmfm)2] and 1-
octanol in the initial stages of the reaction. The yield of 2a
markedly increased about 5 h after the start of the reaction
(turnover frequency (TOF) = 2.0h À1, 5–8 h), and total turn-
over number (TON) was 16.2 after 50h.
The present catalyst system is also effective for the regio-
and stereoselective linear co-dimerization of styrenes (1a–c)
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Communications
mesitylene
(0.50 mL)
was
placed in a two-necked 20-mL
pyrex flask equipped with a
magnetic stirring bar and
a
reflux condenser under a flow
of argon. The reaction was
carried out at 80–1108C for
24 h with stirring in an argon
atmosphere (balloon). After
the reaction mixture was
cooled, the products were ana-
lyzed by GLC, and isolated by
Kugelrohr distillation, flash
column chromatography on
silica gel (hexane/ethyl acetate
95:5), and/or recycling prepara-
tive HPLC.
Ruthenium-catalyzed co-
dimerization of styrenes with
ethylene:
styrene
(2.0mmol),
A
mixture of the
derivative
[Ru( h6-cot)(h2-
1
Scheme 1. Possible reaction pathways. [Ru]=ruthenium complex.
dmfm)2] (0.10 mmol), 1-propa-
nol (6.0mmol), and mesitylene
(0.50 mL) was placed in a 50-mL stainless-steel autoclave equipped
with a glass liner and a magnetic stirring bar under a flow of argon.
Ethylene was then pressurized to 40atm at room temperature, and
the mixture was magnetically stirred at 1308C for 24 h. After the
reaction mixture was cooled, the products were analyzed by GLC,
and isolated by Kugelrohr distillation, flash column chromatography
on silica gel (hexane/ethyl acetate 95:5), and/or recycling preparative
HPLC.
with ethylene (3). As described previously, co-dimerization of
styrenes with ethylene catalyzed by a transition-metal com-
plex generally gave 3-aryl-1-butenes (hydrovinylation), while
unusual co-dimers, namely (E)-1-aryl-1-butenes (4a–c), were
obtained in good yields and with high selectivity with the
present catalyst system [Eq. (4); figures in the parentheses
give yield of isolated product].
2b: White solid; m.p. 998C; b.p. 1508C (0.10 Torr, Kugelrohr); IR
(neat): n˜ = 2915, 2852, 1512, 1445, 969, 837, 798 cmÀ1 1H NMR
;
(CDCl3, 400 MHz): d = 7.39–7.21 (m, 8H), 6.51 (d, J = 16.0Hz, 1H),
6.34 (dt, J = 7.3, 16.0Hz, 1H,), 2.88 (t, J = 7.8 Hz, 2H), 2.62 (dt, J =
7.3 Hz, 2H), 2.46 ppm (s, 6H); 13C NMR (CDCl3, 100 MHz): d =
138.6, 136.4, 135.1, 134.8, 129.9, 129.0(2C), 128.9 (2C), 128.9, 128.2,
125.7 (2C), 35.6, 35.1, 21.3, 21.2 ppm; MS (EI) m/z 236 [M+]. HRMS
(FAB with meta-nitrobenzyl alcohol): m/z 236.1571 [M+H]+, calcd
for C18H20: 236.1565.
2d: White solid; m.p. 748C, b.p. 1308C (0.10 Torr, Kugelrohr);
1H NMR (CDCl3, 400 MHz): d = 7.29–6.95 (m, 8H), 6.35 (d, J =
15.6 Hz, 1H), 6.12 (dt, J = 6.80, 16.0 Hz, 1H), 2.75 (t, J = 8.00 Hz,
2H), 2.49 ppm (m, 2H); 13C NMR (CDCl3, 100 MHz): d = 161.6 (d,
1JC-F = 244 Hz) 160.9 (d, 1JC-F = 241 Hz), 136.9 (d, 4JC-F = 3.3 Hz), 133.4
(d, 4JC-F = 3.4 Hz), 129.4 (d, 3JC-F = 7.4 Hz, 2C), 129.1, 129.0, 129.0,
In conclusion, we have developed a novel catalyst system
consisting of [Ru(h6-cot)(h2-dmfm)2] in the presence of
primary alcohols to produce unusual head-to-head dimers of
styrenes, namely (E)-1,4-diaryl-1-butenes, as well as linear co-
dimers of styrenes with ethylene, namely (E)-1-aryl-1-
butenes, in good yields with high regio- and stereoselectivity.
3
127.1 (d, JC-F = 8.3 Hz, 2C), 115.0(d, 2JC-F = 21.6 Hz, 2C), 114.8 (d,
2JC-F = 20.8 Hz, 2C), 34.9, 34.8 ppm; MS (EI): m/z 246 [M+], HRMS
(FAB with meta-nitrobenzyl alcohol): m/z 244.1067 [M+H]+, calcd
for C16H14F2: 244.1064.
Experimental Section
General procedures: All manipulations were performed in an argon
atmosphere by standard Schlenk techniques or in a glove box. All
solvents were distilled under argon with appropriate drying reagents
(sodium or calcium hydride). [{RuCl2(CO)3}2], [RuCl2(h4-cod)]n, and
[{RuCl2(h6-p-cymene)}2] were obtained commercially, and used with-
out further purification. [Ru(h6-cot)(h2-dmfm)2],[15] [Ru(h4-cod)(h6-
cot)],[22] [Ru(h5-C8H11)(h5-C6H5O)]·PhOH,[18] [RuH2(PPh3)4],[23]
[RuHCl(CO)(PPh3)3],[24] [RuCl2(PPh3)3],[25] and [Cp*RuCl(h4-
cod)][26] were prepared as described in the literature. Styrene
derivatives 1a–d were obtained commercially and used without
further purification. The spectral data of 2a,[27] 2c,[28] 4a,[28] 4b,[29] and
4c[30] were consistent with those reported previously. New com-
pounds, 2b and 2d, are characterized below.
Received: April 11, 2007
Published online: June 25, 2007
Keywords: dimerization · ethylene · homogeneouscatalysis·
.
ruthenium · styrenes
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