{"title":"[(tBu2PhP)Ag(μ-OCF3)]2: A Thermally Stable, Light-Insensitive Nucleophilic Reagent for Trifluoromethoxylation","authors":"Daoqian Chen, Yongrui Luo, Long Lu, Qilong Shen","doi":"10.1021/acs.organomet.4c00073","DOIUrl":null,"url":null,"abstract":"Many trifluoromethoxylation approaches often proposed nucleophilic Ag<sup>I</sup>OCF<sub>3</sub> as a key intermediate. However, the structure of this intermediate remains elusive. Herein, the thermally stable, light-insensitive nucleophilic trifluoromethoxylating reagent [Ag(PPh<sup><i>t</i></sup>Bu<sub>2</sub>)(OCF<sub>3</sub>)] (<b>1</b>) was prepared and fully characterized. Reagent <b>1</b> reacted with a variety of alkyl electrophiles including benzyl bromodes/chlorides, primary alkyl bromides/iodides/triflates/nosylates, and secondary alkyl bromides/triflates/nosylates in good to excellent yields. Mechanistic investigation by reaction with three enantioenriched secondary alkyl electrophiles suggested that these reactions proceed via an S<sub>N</sub>2 pathway, which is consistent with our original mechanistic hypothesis.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-04-04","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.4c00073","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
Many trifluoromethoxylation approaches often proposed nucleophilic AgIOCF3 as a key intermediate. However, the structure of this intermediate remains elusive. Herein, the thermally stable, light-insensitive nucleophilic trifluoromethoxylating reagent [Ag(PPhtBu2)(OCF3)] (1) was prepared and fully characterized. Reagent 1 reacted with a variety of alkyl electrophiles including benzyl bromodes/chlorides, primary alkyl bromides/iodides/triflates/nosylates, and secondary alkyl bromides/triflates/nosylates in good to excellent yields. Mechanistic investigation by reaction with three enantioenriched secondary alkyl electrophiles suggested that these reactions proceed via an SN2 pathway, which is consistent with our original mechanistic hypothesis.
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.