Highly Modular C1‐Symmetric Chiral (P,N) Ligands with a Stereolabile P Center: Experimental and Theoretical Studies |
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| Authors: | Nicolas Humbert Dr. Evgeny Larionov Luca Mantilli Pradeep Nareddy Dr. Céline Besnard Dr. Laure Guénée Prof. Dr. Clément Mazet |
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| Affiliation: | 1. Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4 (Switzerland), Fax: (+41)?22‐379‐3215;2. Laboratoire de Cristallographie, University of Geneva, Quai Ernest Ansermet 24, 1211 Geneva 4 (Switzerland) |
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| Abstract: | An improved synthesis of a novel class of bidentate (P,N) ligands is presented, the structures of which are characterized by three distinct elements of chirality. The stereoselective installation of the elements of central chirality (at the benzylic carbon and the phosphorus atom) depends on the size of the phosphorus substituent. Thermal inversion of the phosphorus center has been studied experimentally and further correlated by DFT calculations. The potential of these ligands and the role of the phosphorus atom in the asymmetric α‐arylation of aldehydes (Pd) and hydrogenation of allylic alcohols (Ir) have also been investigated. |
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| Keywords: | arylation asymmetric catalysis chirality N,P ligands stereoinversion |
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