Directing-Group-Assisted Non-Strained Ether C–O Bond Homolysis Mediated by Low-Valent Titanium

Ether C–O bonds are typical constituents of organic molecules that are seldom regarded as reactive functional groups except when highly strained. With the assistance of appropriate directing groups, low-valent titanium was found to homolytically cleave non-strained C–O bonds. In particular, a newly designed catechol monoether directing group rendered a route toward the activation of non-benzylic C(sp3)–O bonds. This method has been applied to conventional radical addition reactions to alkenes.