Chapter 24. Selective Transformations Starting from a Diastereomerically Enriched Lithiated Benzylsilane

  1. Prof. Dr. Norbert Auner2 and
  2. Prof. Dr. Johann Weis3
  1. Carsten Strohmann,
  2. Daniel H. M. Buchold,
  3. Kerstin Wild and
  4. Daniel Schildbach

Published Online: 5 MAY 2008

DOI: 10.1002/9783527619924.ch24

Organosilicon Chemistry V: From Molecules to Materials

Organosilicon Chemistry V: From Molecules to Materials

How to Cite

Strohmann, C., Buchold, D. H. M., Wild, K. and Schildbach, D. (2003) Selective Transformations Starting from a Diastereomerically Enriched Lithiated Benzylsilane, in Organosilicon Chemistry V: From Molecules to Materials (eds N. Auner and J. Weis), Wiley-VCH Verlag GmbH, Weinheim, Germany. doi: 10.1002/9783527619924.ch24

Editor Information

  1. 2

    Department of Inorganic Chemistry, University of Frankfurt, Marie-Curie-Straße 11, 60439 Frankfurt am Main, Germany

  2. 3

    Consortium of Electrochemical Industry GmbH, Zielstattstraße 20, 81379 Munich, Germany

Author Information

  1. Institut für Anorganische Chemie, Universität Würzburg Am Hubland, D-97074 Würzburg, Germany Tel.: +49 931 888 4613 — Fax: +49 931 888 4605

Publication History

  1. Published Online: 5 MAY 2008
  2. Published Print: 26 SEP 2003

ISBN Information

Print ISBN: 9783527306701

Online ISBN: 9783527619924

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Keywords:

  • organosilanes;
  • lithium;
  • Si-C cleavage;
  • quantum chemical calculations;
  • stereochemistry

Summary

The solid-state structure of the lithiated (aminomethyl)benzylsilane Me2Si{[R]-[CHLiPh]}(CH2SMP) [(R,S)-2] [CH2SMP = (S)-2-(methoxymethyl)pyrroli-dinomethyl] and the absolute configuration at the stereogenic metalated carbon center of this alkyllithium compound, which is highly diastereomerically enriched in solution, were determined by single-crystal X-ray diffraction methods. By computational methods, the mechanism of the deprotonation of the starting compound, (aminomethyl)benzylsilane 1, as well as the stability of configuration of lithiated (R,S)-2, were examined. The stereochemical course of an integral sequence of further transformations, starting from 1, was experimentally clarified. For the selective reaction of (R,S)-2 with MeI, inversion of the configuration at the metalated carbon center was observed.