Diamidophosphites with remote P∗-stereocentres and their performance in Pd-catalyzed enantioselective reactions

Abstract Diamidophosphite ligands based on 1,1′-bis(hydroxymethyl)ferrocene or N 1 , N 2 -bis(( S )-1-hydroxy-3,3-dimethylbutan-2-yl)oxalamide and bearing 1,3,2-diazaphospholidine rings with stereogenic phosphorus atoms were obtained. The use of these ligands provides up to 96% ee in Pd-catalyzed asymmetric allylations of ( E )-1,3-diphenylallyl acetate, up to 70% ee in Pd-catalyzed desymmetrizations of N , N ′-ditosyl- meso -cyclopent-4-ene-1,3-diol bis-carbamate and up to 80% ee in Pd-catalyzed allylic alkylations of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate. Results obtained with a diamidophosphite containing an oxalamide framework show the considerable potential of such ligands in enantioselective catalysis.