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[1] Bienz perfected this approach by means of a coordinating donor tethered to the chiral silicon moiety: S. Bienz, Chimia 1997, 57, 133-139.
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29344432445
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Of course, this rough comparison neglects the distinct spacial arrangements of several ligands in the respective transition states.
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0000004483
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b) for a theoretical study of a platinum-catalyzed hydrosilylation, see: S. Sakaki, N. Mizoe, M. Sugimoto, Organometallics 1998, 17, 2510-2523.
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29344453615
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Diploma Thesis, Albert-Ludwigs-Universität Freiburg (Germany)
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S. Rendler, Diploma Thesis, Albert-Ludwigs-Universität Freiburg (Germany), 2004.
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29344436838
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S. Rendler, M. Oestreich, unpublished results, 2005.
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48
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11844293829
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Such a σ-bond metathesis is likely to involve - at least in a transition state - a pentacoordinated silicon of unknown configuration. Remarkably, possible pseudorotation and, hence, racemization is not observed indicating a concerted process. For pseudorotational processes at pentavalent silicon incorporated into a carbocycle, see: E. P. A. Couzijn, M. Schakel, F. J. J. de Kanter, A.W. Ehlers, M. Lutz, A. L. Spek, K. Lammertsma, Angew. Chem. 2004, 116, 3522-3524;
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29344434967
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[22]
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51
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29344468487
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note
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Without knowledge of the configuration of an assumed pentavalent silicon, models are rather meaningless.
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54
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29344473342
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X. Zhang, K. N. Houk, J. L. Leighton, Angew. Chem. 2005, 117, 960-963;
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56
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29344474512
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note
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The exact trigonal-bipyramidal configuration at silicon in the transition states 30 (Scheme 5) and 35 (Scheme 6) is not entirely understood. At least for 30, it seems plausible though that the bulky tertbutyl group will be located in the equatorial position. The bicyclic structures of 30 and 35 are perfectly pre-organized for diastereofacial discrimination of the carbonyl group.
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58
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0035800404
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Angew. Chem. Int. Ed. 2001, 40, 2915-2917.
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59
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29344432672
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