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A modular approach to a new class of phosphinohydrazones and their use in asymmetric allylic alkylation reactions
Authors:Michael Widhalm  Michael Abraham  Vladimir B. Arion  Siret Saarsalu  Uno Maeorg
Affiliation:1. Institute of Organic Chemistry, Faculty of Chemistry, University of Vienna, Währinger Straße 38, A-1090 Wien, Austria;2. Institute of Inorganic Chemistry, Faculty of Chemistry, University of Vienna, Währinger Straße 42, A-1090 Wien, Austria;3. Institute of Chemistry, University of Tartu, Ravila 14a, 50411, Tartu, Estonia
Abstract:A group of five phosphino hydrazones with a pendant binaphthyl unit as a chiral modifier has been synthesized from non-racemic 2,2′-bis(bromomethyl)-1,1′-binaphthyl and 3,3′-diiodo-2,2′-bis(bromomethyl)-1,1′-binaphthyl as the key intermediates. Their efficiency as chiral ligands in palladium-catalyzed allylic alkylation reactions has been investigated showing up to 95% ee under optimized conditions. X-ray diffraction structures of mono- and dimeric Pd complexes are also reported.
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