Ap hosphite-mediated [2,3]-aza-Wittig rearrangement has been developed for the regio-and enantioselective allylic alkylation of six-membered heteroaromatic compounds (azaarenes). The nucleophilic phosphite adducts of N-allyl salts undergo as tereoselective base-mediated aza-Wittig rearrangement and dissociation of the chiral phosphite for overall C À Hf unctionalization of azaarenes.T his method provides efficient access to tertiary and quaternary chiral centers in isoquinoline,q uinoline,a nd pyridine systems,t olerating ab road variety of substituents on both the allyl part and azaarenes.C atalysis with chiral phosphites is also demonstrated with synthetically useful yields and enantioselectivities.