Enantioselective γ-Deprotonation of Alkyl-Substituted O-1,3-Butadien-2-yl Carbamates and Regioselective Asymmetric Homoaldol Reaction

This work presents a facile method for the construction of geometrically defined 1,3‐dien‐2‐yl carbamates. Their highly stereoselective asymmetric deprotonation with the chiral base pair n‐butyllithium/(–)‐sparteine (2) and substitution reactions allows the flexible synthesis of substituted stereoho...

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Veröffentlicht in:	European Journal of Organic Chemistry 2007-07, Vol.2007 (19), p.3179-3190
Hauptverfasser:	Bou Chedid, Roland, Fröhlich, Roland, Wibbeling, Birgit, Hoppe, Dieter
Format:	Artikel
Sprache:	eng
Schlagworte:	(-)-Sparteine Asymmetric synthesis Carbanions Cross-coupling Homoaldol reaction
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creator	Bou Chedid, Roland Fröhlich, Roland Wibbeling, Birgit Hoppe, Dieter
description	This work presents a facile method for the construction of geometrically defined 1,3‐dien‐2‐yl carbamates. Their highly stereoselective asymmetric deprotonation with the chiral base pair n‐butyllithium/(–)‐sparteine (2) and substitution reactions allows the flexible synthesis of substituted stereohomogeneous 1,3‐dienes. Diastereo‐ and enantioselective homoaldol reactions with aldehydes are possible after transmetallation of the lithium species with ClTi(NEt2)3. Intensive investigations for the interpretation of the stereochemical outcome of the reactions of each carbamate are also presented. Comparison of all results shows common properties of the allyllithium intermediates as well as surprising differences, which indicate a strong relationship between the structure of these intermediates and their reactivity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
doi_str_mv	10.1002/ejoc.200700131
format	Article
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subjects	(-)-Sparteine Asymmetric synthesis Carbanions Cross-coupling Homoaldol reaction
title	Enantioselective γ-Deprotonation of Alkyl-Substituted O-1,3-Butadien-2-yl Carbamates and Regioselective Asymmetric Homoaldol Reaction
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