☆ 4.5 Article

Design of Chiral Hydroxyalkyl- and Hydroxyarylazolinium Salts as New Chelating Diaminocarbene Ligand Precursors Devoted to Asymmetric Copper-Catalyzed Conjugate Addition

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY (2009)

Journal

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

Volume -, Issue 13, Pages 1989-1999

Publisher

WILEY-V C H VERLAG GMBH

DOI: 10.1002/ejic.200801243

Keywords

Asymmetric catalysis; Diaminocarbene; Carbene ligands; Ligand design; Conjugate addition; Atropisomerism

Categories

Chemistry, Inorganic & Nuclear

Funding

Centre National de la Recherche Scientifique (CNRS)
Region Bretagne
Ministere de la Recherche et de la Technologic
Agence Nationale de la Recherche (ANR) (CP2D/RDR2 program)

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Abstract

The design and the synthesis of a set of new chiral hydroxyalkyl- and hydroxyaryl-chelating diaminocarbene ligands is reported. Comparative catalytic studies show the importance of the scaffold design around the NHC unit to obtain a high enantiocontrol in Cu-catalyzed asymmetric conjugate addition (ACA). Whereas low selectivities are observed when the stereogenic centre is placed within the N-heterocyclic ring, an interesting match effect can be observed when central chirality is located within both of the two side chains, which enables up to 92 % ee in the catalysis reaction. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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