Stereochemistry of Imine Reduction by a Hydroxycyclopentadienyl Ruthenium Hydride
- 27 January 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 128 (7), 2286-2293
- https://doi.org/10.1021/ja056402u
Abstract
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.Keywords
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