Dataset Information

Catalytic trifluoromethylation of iodoarenes by use of 2-trifluoromethylated benzimidazoline as trifluoromethylating reagent.

ABSTRACT: The trifluoromethylation of iodoarenes was accomplished by use of a 2-trifluoromethylbenzimidazoline derivative as the trifluoromethylating reagent and a catalytic amount of Cu(I) in the presence of 2,2'-bipyridyl as the ligand. Through a mechanistic study, we found that the oxidative addition of the iodoarene to the Cu(I)-CF₃ species is the rate-determining step.

SUBMITTER: Uchikura T

PROVIDER: S-EPMC7537379 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

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Catalytic trifluoromethylation of iodoarenes by use of 2-trifluoromethylated benzimidazoline as trifluoromethylating reagent.

Uchikura Tatsuhiro T Kamiyama Nanami N Ishikawa Taisuke T Akiyama Takahiko T

Beilstein journal of organic chemistry 20200930

The trifluoromethylation of iodoarenes was accomplished by use of a 2-trifluoromethylbenzimidazoline derivative as the trifluoromethylating reagent and a catalytic amount of Cu(I) in the presence of 2,2'-bipyridyl as the ligand. Through a mechanistic study, we found that the oxidative addition of the iodoarene to the Cu(I)-CF<sub>3</sub> species is the rate-determining step. ...[more]

PMID: 33082878

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Project description:The incorporation of a trifluoromethyl group into an existing scaffold can provide an effective strategy for designing new drugs and agrochemicals. Among the numerous approaches to trifluoromethylation, radical trifluoromethylation mediated by visible light-driven photoredox catalysis has gathered significant interest as it offers unique opportunities for circumventing the drawbacks encountered in conventional methods. A limited understanding of the mechanism and molecular parameters that control the catalytic actions has hampered the full utilization of photoredox catalysis reactions. To address this challenge, we evaluated and investigated the photoredox catalytic trifluoromethylation reaction using a series of cyclometalated Pt(ii) complexes with systematically varied ligand structures. The Pt(ii) complexes were capable of catalyzing the trifluoromethylation of non-prefunctionalized alkenes and heteroarenes in the presence of CF3I under visible light irradiation. The high excited-state redox potentials of the complexes permitted oxidative quenching during the cycle, whereas reductive quenching was forbidden. Spectroscopic measurements, including time-resolved photoluminescence and laser flash photolysis, were performed to identify the catalytic intermediates and directly monitor their conversions. The mechanistic studies provide compelling evidence that the catalytic cycle selects the oxidative quenching pathway. We also found that electron transfer during each step of the cycle strictly adhered to the Marcus normal region behaviors. The results are fully supported by additional experiments, including photoinduced ESR spectroscopy, spectroelectrochemical measurements, and quantum chemical calculations based on time-dependent density functional theory. Finally, quantum yields exceeding 100% strongly suggest that radical propagation significantly contributes to the catalytic trifluoromethylation reaction. These findings establish molecular strategies for designing trifluoromethyl sources and catalysts in an effort to enhance catalysis performance.

Dataset Information

Catalytic trifluoromethylation of iodoarenes by use of 2-trifluoromethylated benzimidazoline as trifluoromethylating reagent.

Publications

Catalytic trifluoromethylation of iodoarenes by use of 2-trifluoromethylated benzimidazoline as trifluoromethylating reagent.

Similar Datasets

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