Premium
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
Author(s) -
Mata Yvette,
Pàmies Oscar,
Diéguez Montserrat
Publication year - 2009
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200900619
Subject(s) - chemistry , palladium , oxazoline , ligand (biochemistry) , allylic rearrangement , moiety , combinatorial chemistry , catalysis , substitution reaction , stereochemistry , substrate (aquarium) , medicinal chemistry , organic chemistry , receptor , biochemistry , oceanography , geology
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 ( ee s 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.