Carboazidation of chiral allylsilanes: experimental and theoretical investigations

Chemistry : a European Journal
Laurent ChabaudKurt Schenk

Abstract

The carboazidation of chiral allylsilanes has been investigated by varying the nature of the substituents at the silicon center and on the carbon framework. The influence of temperature and the nature of the sulfonyl azide, as well as the stereochemistry of the remote stereogenic center, on the 1,2-diastereocontrol of the process were considered. Good to excellent levels of diastereocontrol were generally observed, with the syn-beta-azidosilane always being formed as the major isomer. An illustration of the value of this methodology has been provided with a short and efficient synthesis of an analogue of castanospermine. EPR spectroscopy was carried out on various beta-silyl radicals providing useful information about their conformations in the ground state. Based on this experimental evidence and DFT calculations, reactant-like transition state models were finally proposed that rationalize the observed 1,2-stereoinduction.

References

May 18, 2000·The Journal of Organic Chemistry·M Sugawara, J i Yoshida
Jul 18, 2001·Journal of the American Chemical Society·C Ollivier, P Renaud
Feb 19, 2002·Chemical Reviews·Ian FlemingDavid Walter
Nov 22, 2002·Organic Letters·Laurent ChabaudPhilippe Renaud
Mar 29, 2003·The Journal of Organic Chemistry·Yannick LandaisSheetal S Surange
Aug 22, 2003·Organic & Biomolecular Chemistry·Dimitrios E Lizos, John A Murphy
Nov 25, 2003·The Journal of Organic Chemistry·Lavinia MarinescuMikael Bols
Apr 13, 2004·The Journal of Organic Chemistry·Philippe PanchaudSarunas Zigmantas
Sep 30, 2004·Organic & Biomolecular Chemistry·Hanne PedersenMikael Bols
Feb 26, 2005·Organic & Biomolecular Chemistry·Christian Marcus PedersenMikael Bols
Jun 9, 2005·Journal of the American Chemical Society·Jérôme WaserErick M Carreira
Jun 17, 2005·Organic Letters·Laurent ChabaudPhilippe Renaud
Mar 11, 2006·The Journal of Physical Chemistry. a·Philippe d'AntuonoYannick Landais
Apr 7, 2006·Organic Letters·Pascal Schär, Philippe Renaud
Apr 22, 2006·The Journal of Organic Chemistry·Philippe JamesYannick Landais
Feb 2, 2001·Angewandte Chemie·Christel Viuf, Mikael Bols

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Citations

Jan 18, 2017·Chemistry : a European Journal·Haitham HassanYannick Landais
Dec 13, 2016·Chemistry : a European Journal·Redouane BeniazzaYannick Landais
Feb 17, 2009·Chemistry : a European Journal·Edouard Godineau, Yannick Landais
Aug 30, 2008·The Journal of Organic Chemistry·Edouard GodineauYannick Landais
Mar 27, 2009·The Journal of Organic Chemistry·Sylvaine CrenKurt Schenk
Nov 19, 2010·Journal of the American Chemical Society·Karin WeidnerPhilippe Renaud
Apr 21, 2011·Organic Letters·Virginie LiautardYannick Landais

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