A Study of BF3-Promoted ortho Lithiation of Anilines and DFT Calculations on the Role of Fluorine-Lithium Interactions

摘要

Synthetic and mechanistic aspects of heteroatom directed ortho metalation(DoM)of aryl substrates(1->2->3->4,Scheme 1)have fascinated organic chemists for more than six decades.A hierarchy of DoM groups has been experimentally established and rationalized in terms of the inductive effect of the heteroatom and its ability to coordinate with the metal,which is usually the Li atom of the base that is used for deprotonation(complex induced proximity effect(CIPE)).