Asymmetric additive-free aryl addition to aldehydes using perhydrobenzoxazines as ligands and boroxins as aryl source.

A highly efficient enantioselective aryl addition to aldehydes using boroxins as aryl source and conformationally restricted perhydro-1,3-benzoxazines as ligands is reported. Both enantiomeric forms of chiral arylphenylmethanols and 1,1'-disubstituted diarylmethanols are afforded with excellent yields and enantioselectivities using the same ligand by means of an appropriate combination of boroxin and aromatic aldehyde. The enantiocontrol is not significantly influenced by electronic effects or steric hindrance, even with substituted boroxins. Very homogeneous ee's are reached when substituted arylboroxins are employed, without the use of any class of additive or pre-treatment.