Photocatalytic Cross-Couplings of Aryl Halides Enabled by <i>o</i>-Phosphinophenolate and <i>o</i>-Phosphinothiophenolate
Ni Shen, Run‐Han Li, Can Liu, Xuzhong Shen, Wei Guan, Rui Shang
Abstract
o-Phosphinophenolate and o-phosphinothiophenolate are potent photocatalysts with strong reducing ability to activate aryl chlorides and bromides under visible light for borylation, arylation, and phosphorylation. Experimental and theoretical studies revealed that the o-diphenylphosphino substituent results in a narrow optical gap and facilitates intersystem crossing to access triplet states, which promote phenolate and thiophenolate to function as effective visible-light-photoredox catalysts. The results presented herein suggest promising utility of synthetically modified phenolates and thiophenolates as photoredox catalysts.
Topics & Concepts
ArylIntersystem crossingBorylationPhotocatalysisCatalysisChemistrySubstituentVisible spectrumPhotochemistryPhotoredox catalysisHalideCombinatorial chemistryMedicinal chemistryOrganic chemistryMaterials scienceSinglet statePhysicsOptoelectronicsAlkylExcited stateNuclear physicsRadical Photochemical ReactionsSulfur-Based Synthesis TechniquesCatalytic Cross-Coupling Reactions