[(tBu2PhP)Ag(μ-OCF3)]2: A Thermally Stable, Light-Insensitive Nucleophilic Reagent for Trifluoromethoxylation

IF 2.9 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Daoqian Chen, Yongrui Luo, Long Lu* and Qilong Shen*, 
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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.

Abstract Image

[(tBu2PhP)Ag(μ-OCF3)]2:一种热稳定、光不敏感的三氟甲氧基化试剂
许多三氟甲氧基化方法经常提出亲核的agocf3作为关键中间体。然而,这种中间体的结构仍然难以捉摸。本文制备了热稳定、光不敏感的亲核三氟甲氧基化试剂[Ag(PPhtBu2)(OCF3)](1),并对其进行了表征。试剂1与各种烷基亲电试剂反应,包括苯溴酸酯/氯化物、伯烷基溴化物/碘化物/三氟酸盐/硝基酸盐和仲烷基溴化物/三氟酸盐/硝基酸盐,收率很高。与3个富集对映体的仲烷基亲电试剂的反应机理研究表明,这些反应是通过SN2途径进行的,这与我们最初的机理假设是一致的。
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来源期刊
Organometallics
Organometallics 化学-无机化学与核化学
CiteScore
5.60
自引率
7.10%
发文量
382
审稿时长
1.7 months
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.
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