{"title":"Deprotection of Benzyl-Derived Groups via Uranyl-Photocatalysis","authors":"Jiaolong Meng, Lei Ji, Xuefeng Jiang","doi":"10.1021/acs.organomet.4c00080","DOIUrl":null,"url":null,"abstract":"To circumvent the hazards associated with flammable/explosive hydrogen and address substrate compatibility issues in reductive systems, we developed a mild method for benzyl deprotection facilitated by uranium under visible light irradiation at ambient conditions. The uranium-oxo species, as a metal-oxo-type photosensitizer, demonstrates compatibility with moisture, enabling benzyl C–H activation through ligand-to-metal charge transfer (LMCT) excitation. Subsequent capture of the benzyl radical by atmospheric oxygen induces oxidation at the benzylic position. Removal of the semiacetal occurs, resulting in C–O bond cleavage under acidic conditions. This methodology, featuring mild conditions and operational convenience, is compatible with moisture and oxygen. It presents a complementary strategy for benzyl deprotection for the synthesis of pharmaceuticals and organic materials.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.organomet.4c00080","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
To circumvent the hazards associated with flammable/explosive hydrogen and address substrate compatibility issues in reductive systems, we developed a mild method for benzyl deprotection facilitated by uranium under visible light irradiation at ambient conditions. The uranium-oxo species, as a metal-oxo-type photosensitizer, demonstrates compatibility with moisture, enabling benzyl C–H activation through ligand-to-metal charge transfer (LMCT) excitation. Subsequent capture of the benzyl radical by atmospheric oxygen induces oxidation at the benzylic position. Removal of the semiacetal occurs, resulting in C–O bond cleavage under acidic conditions. This methodology, featuring mild conditions and operational convenience, is compatible with moisture and oxygen. It presents a complementary strategy for benzyl deprotection for the synthesis of pharmaceuticals and organic materials.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.