COMMUNICATIONS
Joan Gallardo-Donaire et al.
Scheme 2. Possible alcohol amination pathway for the synthesis of primary amines.
selectivity, presumably by imine activation. Moreover,
our precatalyst and ligand are both commercially
available and inexpensive. Further mechanistic studies
and the development of an enantioselective version
are currently underway.
Chem. 2010, 122, 8303–8306; Angew. Chem. Int. Ed.
2010, 49, 8126–8129; c) D. Pingen, C. Müller, D. Vogt,
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D. Vogt, ChemCatChem 2013, 5, 2905–2912.
Experimental Section
General Procedure for the Reductive Amination of
Acetophenone Derivatives
Inside the glove box, carbonylchlorohydridotris(triphenyl-
phosphine)ruthenium(II) 28.3 mg (0.0298 mmol) catalyst,
ethylenebis(diphenylphosphine) 12.6 mg (0.0326 mmol),
Al(OTf)3 141 mg (0.297 mmol), freshly distilled and de-
gassed acetophenone 2 0.35 mL (2.97 mmol), degassed and
dried dodecane (674 mL) together with dried and degassed
anhydrous toluene (20 mL) were added to a 100-mL auto-
clave. The autoclave was taken out of the glove box and
pressurised up to 6 bar of NH3 (2 g, 40 equiv.). Then the au-
toclave was pressurised with 40 bar of H2 (total pressure 45–
46 bars). The reaction mixture was stirred for 16 h at 1208C.
Then, the mixture was allowed to cool to room temperature
and an aliquot of the crude reaction mixture (1,5 mL) was
filtered through a plug of celite and analysed by GC and
GC-MS.
[4] For insightful mechanistic studies on alcohol amination,
see: a) D. Pingen, M. Lutz, D. Vogt, Organometallics
2014, 33, 1623–1629; b) D. Pingen, T. Lebl, M. Lutz,
G. S. Nichol, P. C. J. Kamer, D. Vogt, Organometallics
2014, 33, 2798–2805; c) X. Ye, P. N. Plessow, M. K.
Brinks, M. Schelwies, T. Schaub, F. Rominger, R. Pa-
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P. N. Plessow, M. Schelwies, M. K. da Silva, T. Schaub,
Organometallics 2015, 34, 1872–1881.
[5] K. S. Hayes, Appl. Catal. A 2001, 221, 187–195.
[6] For selected reviews, see: a) S. Gomez, J. A. Peters, T.
Maschmeyer, Adv. Synth. Catal. 2002, 344, 1037–1057;
b) T. C. Nugent, M. El-Shazly, Adv. Synth. Catal. 2010,
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[7] T. Gross, A. M. Seayad, M. Ahmad, M. Beller, Org.
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[8] T. Riermeier, K. Haack, U. Dingerdissen, A. Boerner,
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Acknowledgements
CaRLa (Catalysis Research Laboratory) is being co-financed
by the Ruprechts-Karls-University Heidelberg (University of
Heidelberg) and BASF SE.
[12] For the use of [Ru(CO)ClH(PPh3)3] in combination
with ammonia, see: a) S. Imm, S. Bähn, M. Zhang, L.
Neubert, H. Neumann, F. Klasovsky, J. Pfeffer, T. Haas,
M. Beller, Angew. Chem. 2011, 123, 7741–7745; Angew.
Chem. Int. Ed. 2011, 50, 7599–7603; b) W. Baumann,
A. Spannenberg, J. Pfeffer, T. Haas, A. Kçckritz, A.
Martin, J. Deutsch, Chem. Eur. J. 2013, 19, 17702–
17706; c) D. Pingen, M. Lutz, D. Vogt, Organometallics
2014, 33, 1623–1629.
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[13] See the Supporting Information for further details.
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362
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Adv. Synth. Catal. 2016, 358, 358 – 363