Homogeneous Catalytic Hydrogenation of Amides to Amines

Coetzee, Jacorien; Dodds, Deborah L.; Klankermayer, Jürgen; Brosinski, Sandra; Leitner, Walter; Slawin, Alexandra M. Z.; Cole-Hamilton, David J.

doi:10.1002/chem.201204270

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Homogeneous Catalytic Hydrogenation of Amides to Amines

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Leitner, Walter
Institut für Technische und Makromolekulare Chemie RWTH Aachen University;
Service Department Leitner (Technical Labs), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Coetzee, J., Dodds, D. L., Klankermayer, J., Brosinski, S., Leitner, W., Slawin, A. M. Z., et al. (2013). Homogeneous Catalytic Hydrogenation of Amides to Amines. Chemistry - A European Journal, 19(33), 11039-11050. doi:10.1002/chem.201204270.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0014-C9D8-8

Abstract

Hydrogenation of amides in the presence of [Ru(acac)₃] (acacH=2,4-pentanedione), triphos [1,1,1-tris- (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from [Ru(acac)₃], triphos and MSA, or from reactions of [RuX(OAc)(triphos)] (X=H or OAc) or [RuH₂(CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc-κ¹O)₂(H₂O)(triphos)], [Ru(OAc-κ²O,O′)(CH₃SO₃-κ¹O)(triphos)], [Ru(CH₃SO₃-κ¹O)₂(H₂O)(triphos)] and [Ru₂(μ-CH₃SO₃)3(triphos)₂][CH₃SO₃], whereas other complexes, such as [Ru(OAc-κ¹O)(OAc-κ²O,O′)(triphos)], [Ru(CH₃SO₃-κ¹O)(CH₃SO₃-κ²O,O′)(triphos)], H[Ru(CH₃SO₃-κ¹O)₃(triphos)], [RuH(CH₃SO₃-κ¹O)(CO)(triphos)] and [RuH(CH₃SO₃-κ²O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.