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Homogeneous Catalytic Hydrogenation of Amides to Amines
Author(s) -
Coetzee Jacorien,
Dodds Deborah L.,
Klankermayer Jürgen,
Brosinski Sandra,
Leitner Walter,
Slawin Alexandra M. Z.,
ColeHamilton David J.
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201204270
Subject(s) - triphos , chemistry , medicinal chemistry , catalysis , ruthenium , methanesulfonic acid , stereochemistry , organic chemistry
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 [RuH 2 (CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc‐κ 1 O) 2 (H 2 O)(triphos)], [Ru(OAc‐κ 2 O,O′)(CH 3 SO 3 ‐κ 1 O)(triphos)], [Ru(CH 3 SO 3 ‐κ 1 O) 2 (H 2 O)(triphos)] and [Ru 2 (μ‐CH 3 SO 3 ) 3 (triphos) 2 ][CH 3 SO 3 ], whereas other complexes, such as [Ru(OAc‐κ 1 O)(OAc‐κ 2 O,O′)(triphos)], [Ru(CH 3 SO 3 ‐κ 1 O)(CH 3 SO 3 ‐κ 2 O,O′)(triphos)], H[Ru(CH 3 SO 3 ‐κ 1 O) 3 (triphos)], [RuH(CH 3 SO 3 ‐κ 1 O)(CO)(triphos)] and [RuH(CH 3 SO 3 ‐κ 2 O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.