ORGANIC
LETTERS
2011
Vol. 13, No. 15
3774–3777
[3]Rotaxane-Based Dinuclear Palladium
Catalysts for Ring-closure MizorokiÀHeck
Reaction
Yuji Suzaki, Kyoichi Shimada, Eriko Chihara, Takashi Saito, Yoshitaka Tsuchido, and
Kohtaro Osakada*
Chemical Resources Laboratory R1-3, Tokyo Institute of Technology, 4259 Nagatsuta,
Midori-ku, Yokohama 226-8503, Japan
Received March 8, 2011
ABSTRACT
[3]Rotaxane containing two Pd centers in the cyclic compounds catalyzes a MizorokiÀHeck reaction of substrates with two iodophenyl groups
with bisacrylate. Formation of the cyclic products is enhanced by the rotaxane catalyst more smoothly than Pd(OAc)2.
Mechanically interlocked molecular systems such as
rotaxanes and catenanes have attracted increasing atten-
tion due to the unique bonding and structure and a
prototype of molecular machines.1À3 Rotaxane-based mole-
cular shuttles4,5 are employed as intelligent materials such
as molecular devices,6 solids with functional surface,7 and
topological gels.8 There have been fewer reports
for rotaxanes bearing a reactive site.9À11 Epoxidation of
polybutadiene9 and asymmetric hydrogenation of ena-
mides11 were achieved by using rotaxanes containing
manganese porphyrin and a Rh complex, as the respective
catalysts. Reactions involving transformation of the rotax-
ane structure were also reported.12À14 Rotaxanes having
multiple reaction sites would provide the catalysts in which
individual motion of the component molecules changes the
structure and relative position of the active sites. Here we
report catalyst with the [3]rotaxane structure containing
two cyclic components equipped with a Pd center. The
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10.1021/ol201357b
Published on Web 06/28/2011
2011 American Chemical Society