Study On Oxyarylation Of Olefins Catalyzed By Phenolate Anion Under Visible Light

Vicinal difunctionalization of olefins is an important research area in industry as well as in academia.Among them,intermolecular oxyarylation has attracted great attention since one oxygen substituent and one aryl group add across an olefin in a multicomponent coupling process.Although transition-metal catalyzed oxyarylation and Meerwein-type radical oxyarylation methods have been extensively studied for several decades,the ability to access this molecular scaffold array with modular flexibility remains limited.Requiring the use of toxic,unstable,or unavailable aryl precursors(i.e.arylstannanes,aryl diazonium salts,and aryl hydrazines)has impeded the further adaptation of these methods in the synthetic community.In this dissertation,our works mainly focus on the development of visible-light-promoted photocatalytic system for the intermolecular oxyarylation of olefins with stable and readily available(hetero)aryl halides.The first part of this dissertation expounds the research progress on transition-metal catalyzed oxidative oxyarylation and Meerwein-type radical oxyarylation of olefins.The second part introduce an novel and efficient photocatalytic protocol for the intermolecular oxyarylation of a wide range of olefins with non-activated(hetero)aryl halides.Numerous mechanistic studies revealed that the in-situ colored phenolate anions acted as strong reducing photocatalysts in this reaction for the catalytic generation of(hetero)aryl radicals from(hetero)aryl halides under visible light irradiation.This process utilized stable and readily available halogenated arenes as radical precursors and exhibited broad functional group tolerance.The utility of this reaction was further highlighted by the diversified chemical manipulation of the resulting oxyarylation products and the late-stage modification of active pharmaceutical ingredients.