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Pyranoside Phosphite‐Oxazoline Ligand Library: Highly Efficient Modular P,N Ligands for Palladium‐Catalyzed Allylic Substitution Reactions. A Study of the Key Palladium Allyl Intermediates
Authors:Yvette Mata  Oscar Pmies  Montserrat Diguez
Abstract:We have screened a library of modular phosphite‐oxazoline ligands for asymmetric allylic substitution reactions. The library is efficiently prepared from the commercially available and cheap D ‐glucosamine. The introduction of a phosphite moiety into the ligand design is highly advantageous for the product outcome. Therefore, this ligand library affords good‐to‐excellent reaction rates TOFs up to 600 mol substrate×(mol Pd×h)?1] and enantioselectivities (ees up to 99%) and, at the same time, shows a broad scope for mono‐, di‐ and trisubstituted linear hindered and unhindered substrates and cyclic substrates. The NMR studies on the palladium allyl intermediates provide a deeper understanding about the effect of the ligand parameters on the origin of enantioselectivity.
Keywords:allylic substitution  asymmetric catalysis  carbohydrate ligands  P  N ligands  palladium
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