Directed B–H functionalization of the closo-dodecaborate cluster via concerted iodination–deprotonation: reaction mechanism and origins of regioselectivity

Abstract

Understanding the reaction mechanism and regioselectivity control is critical for the rational synthesis of functionalized boron clusters. Herein we report a computational mechanistic study on the phenyliodo diacetate-mediated B–H functionalization of the amide-substituted closo-dodecaborate cluster. A concerted iodination–deprotonation process was identified for the key B–H bond iodination, which is the mechanistic basis for the exceptional regioselectivity of ortho-B–H functionalization. This mechanistic model highlights a distinctive reaction channel for iodine(III)-promoted transformations, which paves the way for future design of directing groups in closo-dodecaborate derivatization using this strategy.