Ph
Cl
OTf
Ph
Cl
Me
Me
Me
Me
2b
5
Me Me
Me Me
Me
Me
Me
Me
Me Me
Ru Ru
Me Me
Ru Ru
Me
PriS
Me
Me
PriS
Me
CH2ClCH2Cl
80 °C, for 2 h
SPri
SPri
Cl H2O
Cl Cl
1
4
Scheme 2
the reactivities of allylic alcohols have been investigated in
detail. The allylation of p-xylene, anisole, toluene and benzene
with allylic alcohols afforded the corresponding allylic aromatic
compounds in good yields. Typical results are given in Table 2.
It is noteworthy that both 1-phenylprop-2-en-1-ol and 2c react
with p-xylene to give the same product, 3. This suggests that a
common (p-allyl)diruthenium complex is formed as an inter-
mediate. The reactions of anisole and toluene with cinnamyl
Footnote
† Detailed experimental results will be reported in due course.
References
1 G. Su¨ss-Fink and G. Meister, Adv. Organomet. Chem., 1993, 35, 41; in
Metal Clusters in Catalysis, ed. B. C. Gates, L. Guzci and V. H.
Kno¨zinger, Elsevier, Amsterdam, 1986.
alcohol produced
a
12:0:88 (o:m:p) mixture of
2 M. Hidai, Y. Mizobe and H. Matsuzaka, J. Organomet. Chem., 1994,
473, 1 and references cited therein; Z. Tang, Y. Nomura, Y. Ishii,
Y. Mizobe and M. Hidai, Organometallics, 1997, 16, 151; K.
Hashizume, Y. Mizobe and M. Hidai, Organometallics, 1996, 15, 3303;
M. Nishio, H. Matsuzaka, Y. Mizobe and M. Hidai, Angew. Chem., Int.
Ed. Engl., 1996, 35, 872; K. Hashizume, Y. Mizobe and M. Hidai,
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H. Matsuzaka, Y. Takagai and M. Hidai, Organometallics, 1994, 13,
13.
4 A. Takahashi, Y. Mizobe and M. Matsuzaka, S. Dev and M. Hidai,
J. Organomet. Chem., 1993, 456, 243.
5 S. Kuwata, Y. Mizobe and M. Hidai, Inorg. Chem., 1994, 33, 3619.
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7 J.-P, Qu¨, H. Matsuzaka, Y. Ishii and M. Hidai, Chem. Lett., 1996,
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8 For an example, see Comprehensive Organometallic Chemistry II, ed.
E. W. Abel, G. A. Stone and G. Wilkinson, Pergamon, Oxford, vol. 12,
1995.
(E)-cinnamylmethoxylbenzenes in 59% total yield (run 3) and a
0:65:35 (o:m:p) mixture of (E)-cinnamylmethyl benzenes in
52% total yield (run 4). Interestingly, the reaction between cis-
cinnamyl alcohol and p-xylene proceeded very slowly at 140 °C
resulting in the formation of 3 in poor yield. This is in sharp
contrast to the reaction of trans-cinnamyl alcohol 2c (vide
supra).
Treatment of 1 with 5 equiv. of cinnamyl chloride 2b in
1,2-dichloroethane at 80 °C for 2 h gave the cationic dinuclear
ruthenium complex [(C5Me5)Ru(SPri)Cl]2[OTf] 4 in 29% yield,
together with an allylated cinnamyl chloride 5 (Scheme 2). The
structure of the paramagnetic complex 4 has been fully
characterized by X-ray crystallography.† Complex 4 can also be
used as a catalyst for the allylation of arenes with allylic
alcohols (Table 2, run 7).
As described above, toluene was mainly allylated at the 3-
and 4-positions (Table 2, run 4). This suggests that the reaction
does not proceed via classical electrophilic aromatic substitu-
tion. Although the reaction mechanism is not yet clear, we
assume that the first step involves the formation of a
(p-allyl)diruthenium complex, which is followed by attack of
arenes on the p-allyl moiety. In connection with this, the
stereochemistry of the allyl moiety in allylated products was
completely controlled, in contrast to the Lewis acid-catalysed
allylation reactions of aromatic compounds.11 This allylation of
arenes with allylic alcohols using diruthenium complexes
provides a new methodology for carbon–carbon bond forma-
tion. Molybdenum- and tungsten-catalysed allylation of aro-
matic compounds has very recently been reported, however, the
catalytic activities of thiolate-bridged diruthenium complexes
are much better than those of molybdenum and tungsten
complexes.12 Further studies on the detailed reaction mechan-
ism and the application to organic synthesis are now in
progress.
9 T. Hayashi, M. Konishi, K. Yokota and M. Kumada, J. Organomet.
Chem., 1985, 285, 359.
10 T. Kondo, H. Ono, N. Satake, T. Mitsudo and Y. Watanabe,
Organometallics, 1995, 14, 1945.
11 T. Tsuchimoto, K. Tobita, T. Hiyama and S. Fukuzawa, Synlett, 1996,
557 and references cited therein.
12 I. Shimizu, T. Sakamoto, S. Kawaragi, Y. Maruyama and A. Yamamoto,
Chem. Lett., 1997, 137.
Received in Cambridge, UK, 17th February 1997; Com.
7/01115F
860
Chem. Commun., 1997