Synthesis and Optical Resolution of Configurationally Stable Zwitterionic Pentacoordinate Silicon Derivatives

Thomas Deis (1) , Julien Maury (1) , Fabrizio Medici (1) , Marion Jean (2) , Jérémy Forte (1) , Nicolas Vanthuyne (2) , Louis Fensterbank (1) , Gilles Lemière (1)

1 IPCM - Institut Parisien de Chimie Moléculaire
2 ISM2 - Institut des Sciences Moléculaires de Marseille

Stereogenic silicon centres in functionalized tetracoordinated organosilanes generally exhibit very high configurational stability under neutral conditions. This stability drops completely when higher coordination states of the silicon center are reached due to rapid substituent exchange. Herein we describe the synthesis of chiral and neutral pentacoordinate silicon derivatives with high configurational stability. The zwitterionic nature of these air and water tolerant species allows for the first time their direct and efficient optical resolution using chiral HPLC techniques. By means of this method, pentacoordinate silicon compounds exhibiting high Si-inversion have been obtained as single enantiomers. A rationalisation of the enantiomerisation pathways has been also carried out using DFT calculations.

Mots clés: silicon; chirality; zwitterion; Chiral HPLC; Optical Resolution

Domaines: Chimie

Thomas Deis, Julien Maury, Fabrizio Medici, Marion Jean, Jérémy Forte, et al.. Synthesis and Optical Resolution of Configurationally Stable Zwitterionic Pentacoordinate Silicon Derivatives. Angewandte Chemie International Edition, 2022, 61 (3), pp.e202113836. ⟨10.1002/anie.202113836⟩. ⟨hal-03440769⟩