Palladium allyl phosphino-oxazoline

On the other hand, palladium(0)-catalyzed allylic animation of racemic ( )-l,3-diphenyl-2-propenyl-l-acetate with the sodium salt of 4-toluenesulfonamide in the presence of phosphino-oxazoline F works very well and affords 14 [96% yield configuration presumably (7 )] of 97% enantiomeric excess, as determined by HPLC77. Remarkably, ligand F also enables a highly enantioselcctivc (up to 90% cc) allylic substitution of racemic 1,3-dialkyl substituted 2-propcnyl-1-carbonates and phosphates using the sodium salt of 4-toluenesulfonamide as nucleophile77. 

Tridentate salen ligands (10) derived from 1 have given excellent results in the enantiocontrol of the hetero Diels-Alder addition reaction of dienes with aldehydes (eq 7) and in the asymmetric additions of TMS-azide to mc5o-epoxide and trimethylsilyl cyanide to benzaldehyde (up to 85% ee). Phosphino-oxazolines derived from 1 have been employed for the asymmetric control of palladium-catalyzed allylic substitution reactions products of 70-90% ee were obtained. Photolysis of crystalline adducts of enantiomerically pure 1 with prochiral alcohols results in asymmetric inductions of up to 79% in a rare example of a solid-state enantioselective reaction. ... 

---