TY - JOUR
T1 - Homogeneous catalytic hydrogenation of amides to amines
AU - Coetzee, Jacorien
AU - Dodds, Deborah Louise
AU - Klankermayer, Juergen
AU - Brosinski, Sandra
AU - Leitner, Walter
AU - Slawin, Alexandra Martha Zoya
AU - Cole-Hamilton, David John
PY - 2013/8/12
Y1 - 2013/8/12
N2 - 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.
AB - 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.
KW - amide hydrogenation
KW - amines
KW - catalysis
KW - homogeneous catalysis
KW - ruthenium
KW - MILD CONDITIONS
KW - RUTHENIUM
KW - REDUCTION
KW - ALCOHOLS
KW - COMPLEXES
KW - BEHAVIOR
KW - CRYSTAL
KW - LIGANDS
KW - ESTERS
UR - http://www.scopus.com/inward/record.url?eid=2-s2.0-84881250006&partnerID=8YFLogxK
U2 - 10.1002/chem.201204270
DO - 10.1002/chem.201204270
M3 - Article
AN - SCOPUS:84881250006
SN - 0947-6539
VL - 19
SP - 11039
EP - 11050
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 33
ER -