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

Organometallics, Journal Year: 2024, Volume and Issue: unknown

Published: April 4, 2024

Many trifluoromethoxylation approaches often proposed nucleophilic AgIOCF3 as a key intermediate. However, the structure of this intermediate remains elusive. Herein, thermally stable, light-insensitive trifluoromethoxylating reagent [Ag(PPhtBu2)(OCF3)] (1) was prepared and fully characterized. Reagent 1 reacted with variety alkyl electrophiles including benzyl bromodes/chlorides, primary bromides/iodides/triflates/nosylates, secondary bromides/triflates/nosylates in good to excellent yields. Mechanistic investigation by reaction three enantioenriched suggested that these reactions proceed via an SN2 pathway, which is consistent our original mechanistic hypothesis.

Language: Английский

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C(sp³)–H Carboxylation via Carbene/Photoredox Cooperative Catalysis

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(2), P. 1287 - 1293

Published: Jan. 7, 2025

C(sp3)–H bond functionalization is a powerful strategy for the synthesis of organic compounds due their abundance in simple starting materials. Photoredox catalysis has led to diverse array enabling activation strategies; however, general platform direct carboxylic acid derivatives remains elusive. Disclosed herein development cooperative NHC/photoredox-catalyzed esterification transformation. This method enables access benzylic, α-heteroatom, and formal β-esterification products moderate high yields under mild reaction conditions.

Language: Английский

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Radical trifluoromethoxylation of fluorinated alkenes for accessing difluoro(trifluoromethoxy)methyl groups

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

In this study, we explore the potential of difluoro(trifluoromethoxy)methyl group, CF 2 –O–CF 3 , an underexplored but promising structural analog trifluoromethoxy group (OCF ).

Language: Английский

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Copper(I) Iodide-Catalyzed Perfluoroalkoxylation Reaction of Alkyl Halides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(34), P. 7139 - 7143

Published: Aug. 15, 2024

We report an efficient perfluoroalkoxylation reaction of alkyl halides catalyzed by copper(I) iodide (CuI), which facilitates the simultaneous activation both perfluoroalkoxide and halides. This methodology is tolerant a wide range functional groups eliminates need for costly metal reagents. The conducted in single step under mildly practical conditions.

Language: Английский

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Palladium Nano-Dispersed and Stabilized in Organically Modified Silicate as a Heterogeneous Catalyst for the Conversion of Aldehydes into O-Silyl Ether Derivatives under Neat Conditions

Synthesis, Journal Year: 2024, Volume and Issue: 56(13), P. 2031 - 2046

Published: May 14, 2024

Abstract Palladium nanoparticles are dispersed and stabilized in organically modified silicate (Pd@MTES), characterized by a number of spectroscopic techniques, including FTIR, TEM, SEM, XPS. The catalytic effect this material toward the hydrosilylation aldehydes ketones is explored, scope reaction investigated, with 26 examples provided. This proceeds under neat conditions via heterogeneous catalysis, mechanistic pathway supported DFT calculations proposed.

Language: Английский

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Phenylseleno trifluoromethoxylation of alkenes

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2434 - 2441

Published: Sept. 26, 2024

Trifluoromethoxylated molecules and selenylated compounds find a wide range of interesting applications, but separately. In order to combine the potential these two motifs propose new class compounds, we have developed an electrophilic phenylseleno trifluoromethoxylation alkenes, which leads β-selenylated trifluoromethoxylated or, upon subsequent reduction, ones.

Language: Английский

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