Stereochemistry of imine reduction by a hydroxycyclopentadienyl ruthenium hydride.
The stereochemistry of hydrogen transfer from [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COD)]Ru(CO)(2)D to N-aryl imines to give amine complexes was shown to be mostly trans stereospecific. Stereospecific hydrogen transfer is proposed to generate an amine and a coordinatively unsaturated ruthenium intermediate in close proximity. Coordination of the amine is proposed to occur faster than lone pair inversion of the amine. In contrast, hydrogen transfer to N-alkyl imines is stereorandom. It is proposed that stereochemistry is lost in part due to the reversibility of the hydrogen transfer being faster than amine coordination.
Department of Chemistry, University of Wisconsin, Madison, WI 53706, USA. casey@chem.wisc.edu
Charles P
CP
Casey
Galina A
GA
Bikzhanova
Ilia A
IA
Guzei
D041961:Deuterium Exchange Measurement; D007097:Imines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013816:Thermodynamics
D007097:Imines; D009942:Organometallic Compounds; C506828:hydroxycyclopentadienyl ruthenium hydride