Modular phosphite-oxazoline/oxazine ligand library for asymmetric pd-catalyzed allylic substitution reactions: scope and limitations-origin of enantioselectivity.
A library of phosphite-oxazoline/oxazine ligands L1-L15 a-h 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 amino acid derivatives. Their modular nature enables the substituents/configurations in the oxazoline/oxazine moiety, alkyl backbone chain and 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 99 %) and good activities have been achieved in a broad range of mono- and disubstituted linear hindered and unhindered liner and cyclic substrates. The NMR studies on the Pd-pi-allyl intermediates provide a deeper understanding about the effect of the ligand parameters on the origin of enantioselectivity. It also indicates that the nucleophilic attack takes place predominantly at the allylic terminal carbon atom located trans to the phosphite moiety.
Diéguez
Montserrat
M
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili. Campus Sescelades, C/Marcel*lí Domingo, s/n. 43007 Tarragona, Spain. montserrat.dieguez@urv.cat
Pàmies
Oscar
O
D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000737:chemistry; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008958:Models, Molecular; D015394:Molecular Structure; D010078:Oxazines / Q000138:chemical synthesis* / Q000737:chemistry; D010080:Oxazoles / Q000138:chemical synthesis* / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D017905:Phosphites / Q000138:chemical synthesis* / Q000737:chemistry; D054852:Small Molecule Libraries; D013237:Stereoisomerism
D000498:Allyl Compounds; D004952:Esters; D008024:Ligands; D010078:Oxazines; D010080:Oxazoles; D017905:Phosphites; D054852:Small Molecule Libraries; D010165:Palladium