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Dalton Transactions
Page 10 of 11
DOI: 10.1039/C5DT04870B
ARTICLE
Journal Name
4
5
Recent reviews, see: (a) S. Bähn, S. Imm, L. Neubert, M.
Zhang, H. Neumann and M. Beller, ChemCatChem, 2011, 3,
1852; (b) C. Gunanathan and D. Milstein, Chem. Rev, 2014,
114, 12024; (c) K. Shimizu, Catal. Sci. Technol, 2015, 5, 1412;
(d) Q. Yang, Q. Wang and Z. Yu, Chem. Soc. Rev, 2015, 44,
2305.
(a) C. Gunanathan and D. Milstein, Angew. Chem. Int. Ed.,
2008, 47, 8661; (b) D. Pingen C. Müller and D. Vogt, Angew.
Chem. Int. Ed., 2010, 49, 8130; (c) S. Imm, S. Bähn, L.
Neubert, H. Neumann and M. Beller, Angew. Chem. Int. Ed.,
2010, 49, 8126; (d) G. Walther, J. Deutsch, A. Martin, F. E.
Baumann, D. Fridag, R. Franke and A. Köckritz,
ChemSusChem, 2011, 4, 1052; (e) W. Baumann, A.
Spannenberg, J. Pfeffer, T. Haas, A. Köckritz, A. Martin and J.
Deutsch, Chem. – Eur. J., 2013, 19, 17702; (f) D. Pingen, O.
Diebolt and D. Vogt, ChemCatChem, 2013, 5, 2905; (g) D.
Pingen, M. Lutz and D. Vogt, Organometallics, 2014, 33,
1623; (h) X. Ye, P.N. Plessow, M. K. Brinks, M. Schelwies, T.
Schaub, F. Rominger, R. Paciello, M. Limbach and P.
Hofmann, J. Am. Chem. Soc., 2014, 136, 5923.
temperature, the autoclave was heated to 165 °C for 15 h with
vigorous stirring (700–800 rpm) without reintroducing NH3 After
cooling to the room temperature, the pressurized NH3 gas in the
autoclave was released in a fume hood. An aliquot of the reaction
mixture was taken for the GC analysis, and the conversion of 1-
octanol and the yield of amine products were calculated based on
GC area %.
Entry 2: RuHCl(CO)(PPh3)3 (45 mg, 0.047 mmol) and triphos (33
mg, 0.052 mmol) were used.
Entry 3: RuHCl(CO)(PPh3)3 (45 mg, 0.047 mmol) was used.
Entry 4: RuHCl(CO){H3CC(CH2PPh2)2[CH2P(p-tol)2]} (38 mg,
0.047 mmol) was used.
Entry 5: RuHCl(CO){H3CC[CH2P(p-tol)2]3} (40 mg, 0.047 mmol)
was used.
Entry 6: RuHCl(CO)(PPh3)3 (45 mg, 0.047 mmol) and CH3C
6
7
E. Balaraman, D. Srimani, Y. D-. Posner and D. Milstein, Catal.
Lett., 2015, 145, 139.
(CH2PPh2)2(2-pyridyl) 4 (26 mg, 0.046 mmol) were used.
Entry 7: RuHCl(CO)(PPh3)[H3CC(CH2PPh2)2(CH2OH)]
0.047 mmol) was used.
E
(41 mg,
(a) S. Imm, S. Bähn, M. Zhang, L. Neubert, H. Neumann, F.
Klasovsky, J. Pfeffer, T. Haas and M. Beller, Angew. Chem.
Int. Ed., 2011, 50, 7599; (b) E. J. Derrah, M. Hanauer, P. N.
Plessow, M. Schelwies, M. K. da Silva and T. Schaub,
Organometallics, 2015, 34, 1872; (c) T. Schaub, B. Buschhaus,
M.K. Brinks, M. Schelwies, R. Paciello, J.P. Melder and M.
Merger, WO2012119927.
(a) H. Heidel, G. Huttner and G. Helmchen, Z. Naturforsch.
1993, 48b, 1681; (b) A. Muth, O. Walter, G. Huttner, A.
Asam, L. Zsolnai and C. Emerich, J. Organomet. Chem., 1994,
468, 149.
Entry 8: The proposed alkoxo-ruthenium complex
F
(20 mg,
0.023 mmol), toluene (8.5 mL), and 1-octanol (1.5 g, 12 mmol)
were used.
Entry 9: RuHCl(CO)(PPh3)3 (45 mg, 0.047 mmol) and CH3C
8
9
(CH2PPh2)2(CH2OMs) 6 (28 mg, 0.052 mmol) were used.
Entry 10: RuHCl(CO)(PPh3)3 (45 mg, 0.047 mmol) and dppdmp
(23 mg, 0.052 mmol) were used.
S. Doherty, E. G. Robins, M. Nieuwenhuyzen, P. A. Champkin
and W. Clegg, Organometallics, 2002, 21, 4147.
Entry 11: RuHCl(CO)(PPh3)3 (45 mg, 0.047 mmol) and dppp (21
mg, 0.052 mmol) were used.
10 (a) T. Seitz, A. Muth and G. Huttner, Chem. Ber., 1994, 127,
1837; (b) Y.–T. Hsieh, C.–M. Cheng, M.–S. Peng and T.–S. Liu,
J. Chem. Soc. Dalton. Trans., 1994, 3499.
11 Attempts to install other diorganophosphino moiety or
heteroatom such as P(o-tolyl)2, P(p-F-C6H4)2, PCy2, PiPr2, and
NH2, were unsuccessful by using our approach.
Entry 12: RuHCl(CO)(PPh3)3 (45 mg, 0.047 mmol), dppp (21 mg,
0.052 mmol), and toluene (6 mL) were used.
Entry 13: RuHCl(CO)(PPh3)3 (45 mg, 0.047 mmol), dppp (21 mg,
0.052 mmol), toluene (6 mL), and p(NH3) = 4 bar (53 mmol of
NH3) were used.
12 K.–M. Sung, S. Huh and J.–M. Jun, Polyhedron, 1999, 18, 469.
13 RuHCl(CO)(triphos) A was characterised by X-ray analysis,
see: S. Savourey, G. Lefèvre, J.-C. Berthert, P. Thuéry, C.
Genre and T. Contat, Angew. Chem. Int. Ed., 2014, 53, 10466.
14 Preparation and characterization of RuHCl(CO)(dppp)(PPh3)
from RuHCl(CO)(PPh3)3 and dppp was reported, see: (a) A.
Santos, J. López, J. Montoya, P. Noheda, A. Romero and A.
M. Echavarren, Organometallics, 1994, 13, 3605; (b) S. Huh,
Y. Cho and J.–M. Jun, Polyhedron, 1994, 13, 1887.
Acknowledgements
CaRLa (Catalyst Research Laboratory) is co-financed by
Ruprechts-Karls-University Heidelberg (Heidelberg University)
and BASF SE.
15 Cyclohexanol and ammonia undergo the selective nomo-
alkylation with dppp ligand. See ref. 4e.
16 In Fig 6, P(NH3) = 4.1 – 4.5 bar was used, which corresponded
to approximately 53 mmol of NH3 in the autoclave.
17 (a) R. Yamaguchi, S. Kawagoe, C. Asai and K. Fujita, Org. Lett.,
2008, 10, 181; (b) R. Kawahara, K. Fujita and R. Yamaguchi, J.
Am. Chem. Soc., 2010, 132, 15108. (c) S. Wöckel, M.
Schelweis, M.K. Brinks, F. Rominger, P. Hofmann and M.
Limbach, Org. Lett. 2013, 15, 266.
18 Program SADABS 2012/1 for absorption correction, see: G.
M. Sheldrick, Bruker Analytical X-Ray Division, Madison,
Wisconsin, 2012.
Notes and references
1
(a) B. R. Brown, The Organic Chemistry of Aliphatic Nitrogen
Compounds, Oxford University, New York, 1994; (b) S. A.
Lawrence, Amines: Synthesis, Properties and Applications,
Cambridge University Press, Cambridge, 2005; (c) P. Roose,
K. Eller, E. Henkes, R. Rossbacher and H. Höke, Amines,
Aliphatic: Ullmann’s Encyclopedia of Industrial Chemistry,
Wiley-VCH, Weinheim, 2015.
2
3
R. N. Salvatore, C. H. Yoon and K. W. Jung, Tetrahedron,
2001, 57, 7785.
(a) J. Kim, H. J. Kim and S. Chang, Eur. J. Org. Chem., 2013,
3201; (b) J. L. Klinkenberg and J. F. Hartwig, Angew. Chem.
Int. Ed., 2011, 50, 86; (c) S. Bähn, S. Imm, L. Neubert, M.
Zhang, H. Neumann and M. Beller, ChemCatChem, 3, 1853.
19 L. Gonzáles-Sebastián, M. Flores-Alamo and J. J. García,
Organometallics, 2012, 31, 8200.
10 | J. Name., 2012, 00, 1-3
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