hydrotalcite, led to highly reactive catalysts. The synthesis of
such heterogeneous systems was very simple and easy to handle.
Textural and spectral characterizations confirmed that ionic
exchange took place without damaging the structure of the
LDH hydrotalcite material. Cycloisomerisation of acetylenic
carboxylic acids to the corresponding 5-membered heterocycles
occurred with 100% atom efficiency, with exclusive formation of
the exo-isomer under heterogeneous conditions. The catalytic Pd
systems were able to sustain the transformation of classical and
more challenging substrates, without addition of an external
base or external ligand in a very short time and at room
temperature. This behaviour can be rationalized by considering
the basicity of the support, which may therefore promote a
clean and selective reaction of acetylenic carboxylic acids. To
the best of our knowledge, these results overcome the ones
obtained using other heterogeneous systems for this reaction,
and are comparable with those obtained under homogeneous
conditions. The easy separation of the product from the
catalyst and further recyclability of the catalysts have also been
demonstrated.
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Acknowledgements
This work was supported by CNCSIS –UEFISCSU, project
number PNII – IDEI 37/2007. COST Action D36 “Molecular
structure-performance relationships at the surface of func-
tional materials” and D24 “Sustainable Chemical Processes:
Stereoselective Transition Metal-Catalyzed Reactions” are also
gratefully acknowledged. This work was also supported by
the Centre National de la Recherche Scientifique (CNRS) and
the Ministe`re de l’Education et de la Recherche for financial
support. We also thank Dr T. Schlama (Rhodia) for a generous
gift of the TPPTS ligand.
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