TY - JOUR T1 - A new class of modular P,N-ligand library for asymmetric Pd-catalyzed allylic substitution reactions: a study of the key Pd-pi-allyl intermediates. AU - Mazuela,Javier, AU - Paptchikhine,Alexander, AU - Tolstoy,Päivi, AU - Pàmies,Oscar, AU - Diéguez,Montserrat, AU - Andersson,Pher G, PY - 2009/11/26/entrez PY - 2009/11/26/pubmed PY - 2010/2/26/medline SP - 620 EP - 38 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 16 IS - 2 N2 - A new class of modular P,N-ligand library has been synthesized and screened in the Pd-catalyzed allylic substitution reactions of several substrate types. These series of ligands can be prepared efficiently from easily accessible hydroxyl-oxazole/thiazole derivatives. Their modular nature enables the bridge length, the substituents at the heterocyclic ring and in the alkyl backbone chain, the configuration of the ligand backbone, and the substituents/configurations in the biaryl phosphite moiety to be easily and systematically varied. By carefully selecting the ligand components, therefore, high regio- and enantioselectivities (ee values up to 96 %) and good activities are achieved in a broad range of mono-, di-, and trisubstituted linear hindered and unhindered substrates and cyclic substrates. The NMR spectroscopic and DFT studies on the Pd-pi-allyl intermediates provide a deeper understanding of the effect of ligand parameters on the origin of enantioselectivity. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/19937621/A_new_class_of_modular_PN_ligand_library_for_asymmetric_Pd_catalyzed_allylic_substitution_reactions:_a_study_of_the_key_Pd_pi_allyl_intermediates_ L2 - https://doi.org/10.1002/chem.200901842 DB - PRIME DP - Unbound Medicine ER -