Oxidative PCET‐Triggered Benzylic C─H Iminolactonization via 1,5‐HAT/Cyclization Enabled by Cage‐Confined Photocatalysis
Abstract
ABSTRACT We present a visible‐light‐driven photocatalytic platform based on a photosensitive metal–organic cage (PMOC), which enables selective recognition and activation of amidyl N─H bonds while suppressing competing homocoupling pathways. This system promotes a controlled intramolecular 1,5‐HAT/cyclization cascade via an oxidative proton‐coupled electron transfer (PCET) process, using commercially available BPO as oxidant and the in situ generated benzoate anion as the base. Mechanistic studies reveal that the cage architecture serves a dual role—facilitating oxidative PCET and enforcing product selectivity through spatial confinement—which steers the reaction through a unimolecular pathway, effectively inhibiting N─N homodimerization typical of bulk‐phase systems. This work establishes cage‐confined photocatalysis as a powerful strategy for directing nitrogen‐centered radical (NCR) reactivity toward the synthesis of value‐added heterocyclic compounds.
Article Details
Authors (8)
Yunqiang Li
Lehn Institute of Functional Materials (LIFM) School of Chemistry Sun Yat‐Sen University Guangzhou P. R. China
Yongxian Huang
GBRCE for Functional Molecular Engineering, MOE Laboratory of Bioinorganic and Synthetic Chemistry, LIFM, IGCME, School of Chemistry
Sisi Huang
Fang Zhang
Key Laboratory of Evolution and Marine Biodiversity (Ministry of Education) and Institute of Evolution and Marine Biodiversity, Ocean University of China, Qingdao, China.
Yingqi Chen
Lehn Institute of Functional Materials (LIFM) School of Chemistry Sun Yat‐Sen University Guangzhou P. R. China
Linna Guo
Instrumental Analysis & Research Center Sun Yat‐Sen University (South Campus) Guangzhou P. R. China
Cheng‐Yong Su
GBRCE For Functional Molecular Engineering Lehn Institute of Functional Materials IGCME School of Chemistry Sun Yat‐Sen University Guangzhou P. R. China
Zhiwei Jiao
GBRCE for Functional Molecular Engineering, MOE Laboratory of Bioinorganic and Synthetic Chemistry, LIFM, IGCME, School of Chemistry