Stereochemistry of Imine Reduction by a Hydroxycyclopentadienyl Ruthenium Hydride

The stereochemistry of hydrogen transfer from [2,5-Ph2-3,4-Tol2(η5-C4COD)]Ru(CO)2D 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...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2006-02, Vol.128 (7), p.2286-2293
Main Authors: Casey, Charles P, Bikzhanova, Galina A, Guzei, Ilia A
Format: Article
Language:English
Subjects:
Chemistry
Deuterium Exchange Measurement
Exact sciences and technology
Imines - chemistry
Labelled compounds chemistry
Magnetic Resonance Spectroscopy
Molecular Conformation
Organic chemistry
Organometallic Compounds - chemistry
Oxidation-Reduction
Reactivity and mechanisms
Stereoisomerism
Thermodynamics
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Summary:The stereochemistry of hydrogen transfer from [2,5-Ph2-3,4-Tol2(η5-C4COD)]Ru(CO)2D 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.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja056402u