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1051
Ghanbaja, J. Appl. Organometal. Chem. 2003, 17, 161–167; (f) Genet, J.-P. Acc.
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dihydrogen was being produced and immediately consumed in the
hydrogenation of the alkene. However, the same author observed
that ReIO2(PPh3)2, ReOCl3(PPh3)2 and MTO did not catalyze the
production of hydrogen from silanes ruling out this possibility
for our system.
It is clear that further studies are needed in order to gain a bet-
ter understanding of the mechanism, mainly by identifying the fate
of the R3Si groups as well as by attempting to identify other Re
containing intermediates or side products.
In conclusion, we have developed, to the best of our knowledge,
the first example of the practical, catalytic hydrogenation of alkenes
tothecorrespondingalkanes bymolecular high-valent oxo-rhenium
(V) and (VII) complexes and a silane. This novel methodology was
successfully applied to the reduction of mono- and disubstituted
olefins, in contrast to the method using silanes catalyzed by PdCl2
or Pd(OAc)2, which only reduced monosubstituted terminal double
bonds.17b,18
An important benefit of this method is that the reduction is
done in the absence of hydrogen gas and high pressures. This novel
method can be carried out in simple, readily available laboratory
equipment, in contrast to catalytic hydrogenation, which demands
handling of hydrogen gas and often requires rather expensive high-
pressure equipment.
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Other advantages of this methodology include high yields, good
chemoselectivity, mild conditions, easy preparation of the cata-
lyst8a and its stability towards air and moisture, allowing the reac-
tion to be carried out under air atmosphere. We believe that this
procedure will be a useful and attractive alternative to the existing
methods for the reduction of alkenes.
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Further mechanistic studies and other synthetic applications of
this catalytic system, including asymmetric hydrogenation of al-
kenes are under investigation in our group.
Acknowledgements
17. (a) Mandal, P. K.; McMurray, J. S. J. Org. Chem. 2007, 72, 6599–6601; (b) Mirza-
Aghayan, M.; Boukherroub, R.; Bolourtchian, M. Appl. Organomet. Chem. 2006,
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18. Mirza-Aghayan, M.; Boukherroub, R.; Bolourtchian, M.; Hossein, M.
Tetrahedron Lett. 2003, 44, 4579–4580.
This research was supported by FCT through project PTDC/QUI/
71741/2006. R.G.N. thanks FCT for a postdoctoral grant (SFRH/BPD/
27215/2006). The NMR spectrometers are part of the National
NMR Network and were purchased in the framework of the Na-
tional Programme for Scientific Re-equipment, contract REDE/
1517/RMN/2005, with funds from POCI 2010 (FEDER) and Fun-
dação para a Ciência e a Tecnologia (FCT).
19. In
a typical experiment, to a mixture of alkene (2.0 mmol) and catalyst
(5 mol %) was added dimethylphenylsilane (200 mol %). The reaction mixture
was stirred at 45 °C under air atmosphere. After 2 h was added more silane
(200 mol %). The progress of the reactions was monitored by 1H NMR. The NMR
yields were determined using toluene (2.0 mmol) as an internal standard.
20. Chung, L. W.; Lee, H. G.; Lin, Z. Y.; Wu, Y. D. J. Org. Chem. 2006, 71, 6000–6009.
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