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Volumn 12, Issue 1, 2005, Pages 30-37

Chirality transfer from silicon to carbon

Author keywords

Allylation; Asymmetric synthesis; Chirality; Hydrosilylation; Silicon

Indexed keywords

CARBON; MATHEMATICAL TRANSFORMATIONS; SILANES; SILICON; STEREOCHEMISTRY; SUBSTITUTION REACTIONS;

EID: 29344469998     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200500782     Document Type: Article
Times cited : (49)

References (61)
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    • note
    • Of course, this rough comparison neglects the distinct spacial arrangements of several ligands in the respective transition states.
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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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    • Couzijn, E.P.A.1    Schakel, M.2    De Kanter, F.J.J.3    Ehlers, A.W.4    Lutz, M.5    Spek, A.L.6    Lammertsma, K.7
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    • note
    • Without knowledge of the configuration of an assumed pentavalent silicon, models are rather meaningless.
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    • note
    • 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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    • In fact, this assumption holds true for an unrelated application of silicon-stereogenic silanes: S. Rendler, G. Auer, M. Oestreich, Angew. Chem. 2005, 117, DOI: 10.1002/ange. 200502631;
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.