Regioselective heterohalogenation of 4-halo-anisoles via a series of sequential ortho-aluminations and electrophilic halogenations.

As the aluminate base [LiAl(TMP)(2)(iBu)(2)] 1 displays halogen tolerance towards substituted aromatics, 4-halo-anisoles have been ortho-aluminated and electrophilically quenched to form synthetically useful multi-heterohalogenated anisoles, with the Al intermediates along the route structurally defined. This journal is © The Royal Society of Chemistry 2012