Phosphites and diamidophosphites based on mono-ethers of BINOL: a comparison of enantioselectivity in asymmetric catalytic reactions

Novel P-monodentate phosphite-type ligands have been synthesized in one step from BINOL mono-tosylate and BINOL mono-(−)-menthylcarbonate. The use of these ligands provides up to 96% ee in Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate and up to 99% ee in Rh-catalyzed asymmetric addition of phenylboronic acid to cyclohex-2-enone. The influence of the structural modules such as the nature of phosphorus-containing ring or exocyclic substituent on the enantioselectivity is discussed.