Semiconductor Cluster with High Reduction Potential and Efficient Charge Transfer Enables Visible‐Light‐Driven Activation of Inert Organic Substrates
Abstract
AbstractPhotoredox catalysis is an essential component of modern organic synthesis. However, current photocatalysts face the challenge of simultaneously requiring strong redox potentials and efficient charge transfer to meet the thermodynamic and kinetic demands of photoinduced electron transfer processes. Herein, we present an excellent reactivity mode for photocatalysis based on semiconductor clusters, exploiting the ideal Marcus parabola to couple potential and kinetic requirements. Our system demonstrates an exceptionally high negative reduction potential (Ered) (−2.94 V versus SCE, on par with K0) and realizes efficient charge transfer—rapid charge separation (CS) and slow charge recombination (CR) kinetics. This duality endows the protocol with remarkable versatility by enabling the dearomatization of nonactivated arenes and reductive dehalogenation of challenging aryl/alkyl chlorides and aryl fluorides, as well as arylation and amination, with a high functional group tolerance under visible‐light irradiation. Furthermore, this platform offers easy recyclability, supports gram‐scale synthesis, and can be extended to the late‐stage functionalization and deuteration of drugs. This innovative catalytic platform provides a new approach for the photochemical activation of inert organic substrates and is foreseen to promote the development of radical reaction‐based pharmaceutical synthesis.
Article Details
Authors (15)
Hao Ma
National Synchrotron Radiation Laboratory
Cheng‐Kun Han
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou 510632 China
Jia‐Xing Liu
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou 510632 China
Yi‐Lei Xu
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou 510632 China
Chao‐Li Chen
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou 510632 China
Xu‐Hang Zhong
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou China
Li‐Yang Chen
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou 510632 China
Rui Zhou
Bingzhe Wang
Jinan University , , , ,
Junhui Wang
Jingyi Zhu
Kaifeng Wu
State Key Laboratory of Chemical Reaction Dynamics and New Cornerstone Science Laboratory
Dong‐Sheng Li
College of Materials and Chemical Engineering Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials China Three Gorges University Yichang China
Tao Wu
Shang‐Fu Yuan
State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science and Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University Guangzhou China