Leveraging Divergent Ligand-to-Metal Charge-Transfer Excited State Pathways for Catalyst Control over Alkoxyl Radical Reactivity.

ABSTRACT: Ligand-to-metal charge-transfer (LMCT) excitation has emerged in recent years as a powerful modality in organic synthesis, namely for the generation of heteroatom-centered radicals through formal metal-ligand bond homolysis from the LMCT excited state. However, the exploitation of alternative LMCT excited state processes has been extremely limited. Here, we describe a general strategy for tuning the reaction course from LMCT excited states of titanium alkoxides. This reactivity paradigm has been exploited for tandem β-scission/Giese addition reactions of both scission-amenable and scission-recalcitrant alcohols under divergent reaction pathways of metal-ligand bond homolysis and excited state β-scission through judicious choice of electronically tuned Ti catalysts. Through intramolecular c

SUBMITTER: Tang Z 

PROVIDER: S-EPMC12919716 | biostudies-literature | 2026 Feb

REPOSITORIES: biostudies-literature