Fernando Pérez‐Maseda, María Martín, Jorge Labrador‐Santiago, Inés Corral, Diego J. Cárdenas
{"title":"Fe‐Photocatalyzed Decarboxylative Giese‐Type Reaction of α‐N, O or S Carboxylic Acids: Insight into the Mechanism of the Radical Formation","authors":"Fernando Pérez‐Maseda, María Martín, Jorge Labrador‐Santiago, Inés Corral, Diego J. Cárdenas","doi":"10.1002/adsc.70114","DOIUrl":null,"url":null,"abstract":"Very simple conditions are described for the Fe‐photocatalyzedaddition of α‐amino, α‐alkoxy, and α‐alkylthio radicals to electron‐deficient alkenes. The reactions proceed under smooth ligandless conditions with inexpensive base and in the absence of oxidant. A mechanistic computational TD‐DFT study on the formation and evolution of the electronic excited states supports for the first time that, after Fe(III)‐carboxylate excitation by visible light, homolytic cleavage of the FeO actually takes place, leading to a carboxyl radical.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"74 1","pages":""},"PeriodicalIF":4.0000,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Synthesis & Catalysis","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/adsc.70114","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
Abstract
Very simple conditions are described for the Fe‐photocatalyzedaddition of α‐amino, α‐alkoxy, and α‐alkylthio radicals to electron‐deficient alkenes. The reactions proceed under smooth ligandless conditions with inexpensive base and in the absence of oxidant. A mechanistic computational TD‐DFT study on the formation and evolution of the electronic excited states supports for the first time that, after Fe(III)‐carboxylate excitation by visible light, homolytic cleavage of the FeO actually takes place, leading to a carboxyl radical.
期刊介绍:
Advanced Synthesis & Catalysis (ASC) is the leading primary journal in organic, organometallic, and applied chemistry.
The high impact of ASC can be attributed to the unique focus of the journal, which publishes exciting new results from academic and industrial labs on efficient, practical, and environmentally friendly organic synthesis. While homogeneous, heterogeneous, organic, and enzyme catalysis are key technologies to achieve green synthesis, significant contributions to the same goal by synthesis design, reaction techniques, flow chemistry, and continuous processing, multiphase catalysis, green solvents, catalyst immobilization, and recycling, separation science, and process development are also featured in ASC. The Aims and Scope can be found in the Notice to Authors or on the first page of the table of contents in every issue.