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A very efficient organocatalytic protocol for the hydrosilylation of ketimines (with ≤92% ee) has been developed by us recently: a) A. V. Malkov, A. Mariani, K. MacDougall, P. Kočovský, Org. Lett. 2004, 6, 2253;
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6] and other metal complexes: A. V. Malkov, I. R. Baxendale, J. Fawcett, D. R. Russel, V. Langer, D. J. Mansfield, M. Valko, P. Kočovský, Organometallics 2001, 20, 673.
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Transfer hydrogenation and oxazaborolidine-catalyzed reduction of ketones with borane have been shown to proceed through a six-membered transition state : a) M. Yamakawa, H. Ito, R. Noyori, J. Am. Chem. Soc. 2000, 122, 1466;
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40
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note
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Replacing the Ph in 6 with tBu led to virtually identical results, which rules out arene-arene interactions of the substrate with the Ph in 6.
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41
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2), see: S. Shambayati, W. E. Crowe, S. L. Schreiber, Angew. Chem. 1990, 102, 273;
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[9d,e] Hayashi and co-workers arrived at a similar conclusion: a) T. Shimada, A. Kina, T. Hayashi, J. Org. Chem. 2003, 68, 6329;
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The geometries of monomers were determined by the cc-pVTZ/ RI-MP2 gradient optimization in the Turbomole v.5.6 package (R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165); the optimized geometries of monomers were kept frozen throughout the scans. Interaction energies were computed with aug-cc-pVDZ basis set at RI-MP2 level in Turbomole v.5.6 and are BSSE-corrected. Only the face-to-face geometry was examined, thus keeping the planes of the monomers parallel throughout the scans.
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