Homogeneous catalytic hydrogenation of amides to amines

Jacorien Coetzee, Deborah Louise Dodds, Juergen Klankermayer, Sandra Brosinski, Walter Leitner, Alexandra Martha Zoya Slawin, David John Cole-Hamilton

Research output: Contribution to journalArticlepeer-review

122 Citations (Scopus)

Abstract

Hydrogenation of amides in the presence of [Ru(acac)] (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 prepared from [Ru(acac) ], triphos and MSA, or from reactions of [RuX-(OAc)(triphos)] (X=H or OAc) or [RuH(CO)(triphos)] with MSA. Crys-tallographically characterised complexes include: [Ru(OAc-κO) (HO)-(triphos)], [Ru(OAc-κO,O') (CHSO-κO)(triphos)], [Ru(CH SO-κO)-(H O)(triphos)] and [Ru(μ-CHSO )-(triphos)][CHSO], whereas other complexes, such as [Ru(OAc-κO)(OAc- κO,O')(triphos)],[Ru(CHSO- κO)(CHSO-κO,O')- (triphos)], H[Ru(CHSO-κO) -(triphos)], [RuH(CHSO-κO) (CO)-(triphos)] and [RuH(CHSO-kO,O')- (triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.
Original languageEnglish
Pages (from-to)11039-11050
Number of pages12
JournalChemistry - A European Journal
Volume19
Issue number33
DOIs
Publication statusPublished - 12 Aug 2013

Keywords

  • amide hydrogenation
  • amines
  • catalysis
  • homogeneous catalysis
  • ruthenium
  • MILD CONDITIONS
  • RUTHENIUM
  • REDUCTION
  • ALCOHOLS
  • COMPLEXES
  • BEHAVIOR
  • CRYSTAL
  • LIGANDS
  • ESTERS

Fingerprint

Dive into the research topics of 'Homogeneous catalytic hydrogenation of amides to amines'. Together they form a unique fingerprint.

Cite this