High-valent Cu(<scp>iii</scp>)–CF<sub>3</sub> compound-mediated esterification reaction

Dai, Ming-Suo; Zheng, Zhen-Mei; Zhang, Songlin

doi:10.1039/d2ob02166h

Cited by 9 publications

(4 citation statements)

References 41 publications

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“…The chemoselectivity is dictated by the basicity of the reaction solutions that controls the fate of a radical cation intermediate to generate either difluorocarbene or N ‐centered radical species. This unusual reactivity of Cu(III)(CF 3 ) 3 compounds with anilines is remarkably distinct from those CF 3 ‐transferring reactivity properties developed previously [20] . This study may inspire the development of other interesting reactions employing Cu(III)(CF 3 ) 3 compounds.…”

Section: Methodsmentioning

confidence: 50%

Base‐Controlled Chemoselective Reaction of High‐Valent Cu(III)−CF₃Compounds with Anilines: Access to Formamides or Hydrazines

et al. 2023

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This study reports reactivity properties of Cu(III)−CF3 compounds with anilines, wherein basicity‐dictated distinct reactivities are achieved, giving rise to formamides or hydrazines. Competing generation of difluorocarbene and N‐centered radical is proposed that is controlled by the basicity of the reaction solution. Specifically, under acidic or neutral conditions, reaction of anilines with Cu(III)−CF3 compounds produces formamides, where difluorocarbene is involved, undergoing aniline formylation. In contrast, in the presence of a base, this same reaction selectively gives hydrazines instead, where Cu(III)−CF3 compounds act as an oxidizing reagent to allow dehydrogenative N−H/N−H coupling of two anilines through an N‐centered radical. The scope of both reactions is studied, and application to medicinally relevant compounds is shown. This study shows the unusual use of high‐valent Cu(III) trifluoromethyl compounds as hydrogen‐abstracting reagents to allow dehydrogenative reactions.

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Section: Methodsmentioning

confidence: 50%

Base‐Controlled Chemoselective Reaction of High‐Valent Cu(III)−CF₃Compounds with Anilines: Access to Formamides or Hydrazines

et al. 2023

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“…In addition to serving as organometallic CF 3 group transfer reagents, Cu(III) trifluoromethyl compounds have recently been shown to be novel coupling reagent to mediate the condensation of carboxylic acdis and alcohols/amines to synthesize esters and amides [10a] . Moreover, they are also efficient oxidizing reagent to promote N−H/N−H cross‐coupling to give hydrazines from amines, [10b] and to mediate oxidation of epoxides by DMSO to give 1,2‐diketones [10c] . These studies demonstrate the versatile reactivity properties and the synthetic potential of high‐valent Cu(III)‐trifluoromethyl compounds in organic synthesis.…”

Section: Methodsmentioning

confidence: 99%

Cu(III)‐CF₃ Compound‐Activated DMSO: An Efficient Oxidizing Reagent to Convert Alcohols to Ketones

Hou,

Zhang

2024

Eur J Org Chem

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In this study high‐valent Cu(III) trifluoromethyl compounds in combination with DMSO is shown to be an efficient and mild oxidizing system for the conversion of alcohols to ketones (aldehydes as well). Trifluoromethoxylated sulfonium species is proposed to be initially formed that engages in crucial steps of alkoxy replacement at sulfonium center and deprotonative collapse of the resulting alkoxysulfonium intermediate in the presence of a base. This reaction is highly selective without over‐oxidation, and can tolerate a broad range of functional groups owing to mild oxidizing ability of the Cu(III)‐CF3/DMSO system and the inert N2 conditions. This method can be applied to the synthesis and functionalization of commercial drug compounds. This study illustrates an unusual reactivity property of high‐valent Cu(III) trifluoromethyl compounds beyond the conventional CF3 group transfer reactivity, and opens up new opportunities for developing novel reactions of Cu(III)‐CF3 compounds. The combined use of high‐valent Cu(III)‐CF3 compound and DMSO is anticipated to find more applications to develop other novel and useful oxidation reactions.

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“…The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/molecules29030570/s1, General information; General procedure for the synthesis of methyl benzoate 5a under solar simulator irradiation; General procedure for the synthesis of methyl benzoate 5a under sunlight irradiation; General procedure to esters under blue LED irradiation; Compound characterizations; Detection and characterization of benzoyl chloride 3; References [25,[55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73]; NMR spectra of esters; NMR spectra of benzoyl chloride (3); UV-Vis spectra.…”

Section: Supplementary Materialsmentioning

confidence: 99%

Visible Light-Promoted Oxidative Cross-Coupling of Alcohols to Esters

Dellisanti,

Chessa,

Porcheddu

et al. 2024

Molecules

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Ester is one of the most significant functional groups in organic chemistry and is enclosed in several valued molecules. Usually, esters are prepared through the acid-catalyzed esterification reaction of carboxylic acids with alcohols, transesterification of esters with alcohols, or via activation of carboxylic acids followed by the addition of alcohols. However, these procedures typically imply the excess use of reactants and harsh reaction conditions. Visible light-mediated photoreactions have been disclosed to display a safe, sustainable, and accessible alternative to traditional methods, and to lead new reactivity modes in organic procedures. In this context, we propose a transition metal-based and organic-based photocatalyst-free synthesis of esters from alcohols induced by visible light. The methodology can be carried out using sunlight or artificial visible light as a solar simulator or a blue LED source.

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High-valent Cu(iii)–CF₃ compound-mediated esterification reaction

Abstract: Cu(III)-CF3 compounds are reported herein as novel coupling reagent to mediate ester synthesis from carboxyl acids and alcohols/phenols. Carboxylic acids are transformed to trifluoromethyl ester and acyl fluoride activated species...

Cited by 9 publications

References 41 publications

Base‐Controlled Chemoselective Reaction of High‐Valent Cu(III)−CF₃Compounds with Anilines: Access to Formamides or Hydrazines

Base‐Controlled Chemoselective Reaction of High‐Valent Cu(III)−CF₃Compounds with Anilines: Access to Formamides or Hydrazines

Cu(III)‐CF₃ Compound‐Activated DMSO: An Efficient Oxidizing Reagent to Convert Alcohols to Ketones

Visible Light-Promoted Oxidative Cross-Coupling of Alcohols to Esters

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High-valent Cu(iii)–CF3 compound-mediated esterification reaction

Abstract: Cu(III)-CF3 compounds are reported herein as novel coupling reagent to mediate ester synthesis from carboxyl acids and alcohols/phenols. Carboxylic acids are transformed to trifluoromethyl ester and acyl fluoride activated species...

Cited by 9 publications

References 41 publications

Base‐Controlled Chemoselective Reaction of High‐Valent Cu(III)−CF3Compounds with Anilines: Access to Formamides or Hydrazines

Base‐Controlled Chemoselective Reaction of High‐Valent Cu(III)−CF3Compounds with Anilines: Access to Formamides or Hydrazines

Cu(III)‐CF3 Compound‐Activated DMSO: An Efficient Oxidizing Reagent to Convert Alcohols to Ketones

Visible Light-Promoted Oxidative Cross-Coupling of Alcohols to Esters

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Product

Resources

About

High-valent Cu(iii)–CF₃ compound-mediated esterification reaction

Base‐Controlled Chemoselective Reaction of High‐Valent Cu(III)−CF₃Compounds with Anilines: Access to Formamides or Hydrazines

Base‐Controlled Chemoselective Reaction of High‐Valent Cu(III)−CF₃Compounds with Anilines: Access to Formamides or Hydrazines

Cu(III)‐CF₃ Compound‐Activated DMSO: An Efficient Oxidizing Reagent to Convert Alcohols to Ketones