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Angewandte
Communications
Sanchez-Delgado, J. Mol. Catal. A 2007, 270, 250 – 256; c) D.
Konya, K. Q. Almeida Lenero, E. Drent, Organometallics 2006,
believe complex A is responsible for the performance of the
present catalytic system.
´
25, 3166 – 3174; d) E. Mieczynska, A. M. Trzeciak, J. J. Ziꢁłkow-
In summary, we have developed an active and selective
ruthenium-based catalyst system for the conversion of
terminal and internal aliphatic and araliphatic alkenes to
linear alcohols by a domino hydroformylation/reduction
reaction sequence. Although ruthenium complexes have
been largely neglected for carbonylations, this work demon-
strates that ruthenium can be an appropriate and promising
metal for such reactions. The results presented here constitute
a useful alternative to the recently reported rhodium-
catalyzed domino hydroformylation/reduction reactions.[19]
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[7] For compendia on ruthenium-catalyzed reactions, see: a) Ruthe-
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Dixneuf), Springer, Heidelberg, 2004; b) S.-I. Murahashi, Ruthe-
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[8] D. Evans, J. A. Osborn, F. H. Jardine, G. Wilkinson, Nature 1965,
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Experimental Section
General method for the optimized hydroformylation/reduction of
alkenes: A 25 mL steel autoclave was charged under argon atmos-
phere with [Ru3(CO)12] (25.6 mg, 40.0 mmol), 2a (36.7 mg, 132 mmol)
and LiCl (212 mg, 5.00 mmol). Then, NMP (3 mL), H2O (1.0 mL,
1.0 g, 56 mmol), and alkene (20.0 mmol) were added. The autoclave
was pressurized with 60 bar CO/H2 and heated to 1308C for 20 h.
After the reaction time, the autoclave was cooled with ice water and
the pressure was released. The crude reaction mixture was analyzed
by gas chromatography with isooctane (2.0 mL) as internal standard.
For isolation of selected compounds, the solvent was removed by
washing the crude reaction mixture with water. Subsequent bulb-to-
bulb distillation afforded the desired product.
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Received: September 3, 2012
Published online: February 12, 2013
[10] K. Takahashi, M. Yamashita, Y. Tanaka, K. Nozaki, Angew.
Chem. 2012, 124, 4459 – 4463; Angew. Chem. Int. Ed. 2012, 51,
4383 – 4387.
Keywords: alcohols · domino reactions ·
.
homogeneous catalysis · hydroformylation · ruthenium
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2010, 82, 635 – 647; b) D. B. Grotjahn, Dalton Trans. 2008, 6497 –
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[1] For recent reviews and compendia on carbonylation reactions,
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[2] For recent reviews on hydroformylations, see: a) K.-D. Wiese, D.
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[12] J. Falbe, H. Bahrmann, W. Lipps, D. Mayer in Ullmannꢀs
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Wiley-WCH, Weinheim, 2009.
[13] P. Kalck, M. Siani, J. Jenck, B. Peyrille, Y. Peres, J. Mol. Catal.
1991, 67, 19 – 27.
À
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Springer, Heidelberg, 2000.
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[15] For more details, see the Supporting Information.
[16] For ruthenium-catalyzed carbonylations in the presence of
water, see: a) J. Jenck, P. Kalck, E. Pinelli, M. Siani, A.
Thorez, J. Chem. Soc. Chem. Commun. 1988, 1428 – 1430;
[3] O. Roelen, DE 849548, 1938/1952; O. Roelen, US 2327066, 1943
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Angew. Chem. Int. Ed. 2013, 52, 2949 –2953