Palladium-catalyzed decarbonylative methylation of aryl carboxylic acids

Feng, Boya; Zhang, Guodong; Xu, Feng

doi:10.1039/d1qo01756j

Cited by 6 publications

(5 citation statements)

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“…However, these methods suffer from some drawbacks, such as the need for a stepwise synthesis of the desired product or using unstable and odorous feedstock. Based on previous research achievements and inspiration, , we believed that the decarbonylative cyanation reaction can be achieved by the transition-metal catalysis in situ activation strategy and applied to carboxylic acids to form aromatic nitriles, which can avoid the need for pre-synthesis of carboxylic acid derivatives in the above methods. Herein, we report a practical and direct one-pot transformation of structurally diverse carboxylic acids with Zn(CN) 2 into aromatic nitriles via metal catalysis in the presence of Piv 2 O as an activator (Scheme e).…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Direct Decarbonylative Cyanation of Aryl Carboxylic Acids

et al. 2022

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The direct transformation of aryl carboxylic acids to aryl nitrile compounds is an interesting topic because carboxylic acids are not only abundant in nature but are also inexpensive and stable. Here, the synthesis of a series of aryl nitriles by palladium-catalyzed decarbonylative cyanation of carboxylic acids without base has been achieved. The successful decarbonylative cyanation of drug molecules and Gram-scale reaction to verify the practicality and operability of this method are analyzed.

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Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Direct Decarbonylative Cyanation of Aryl Carboxylic Acids

et al. 2022

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“…The introduction of the methyl group to drug molecules is helpful to improve their binding affinity, biological availability, and metabolic stability (called “magic methyl effect”), which greatly changes the pharmacological properties of bioactive molecules. − Methylation plays an important role in the modification of drug molecules, DNA, as well as proteins. − According to different reaction mechanisms, the methylation agents are divided into three classes, i.e., electrophilic methylation reagents, nucleophilic methylation reagents, and free radical methylation reagents . At present, great progress has been made in the methylation reaction. − Many chemists have made outstanding contributions in this field, and a large number of new methyl reagents − and new methylation reactions have been developed, − especially electrocatalytic, , visible-light-induced, or transition-metal-catalyzed − methylation, in recent years. In 2021, Dixon and co-workers published an important review about C–H methylation in chemical synthesis, which covered the various methylation reagents and diverse strategies employed to realize the selective installation of the C–Me bond in extensive chemical structures .…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study for Evaluating and Discovering Organic Hydride Compounds as Potential Novel Methylation Reagents

et al. 2022

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Methylation reaction is a fundamental chemical reaction that plays an important role in the modification of drug molecules, DNA, as well as proteins. This work focuses on seeking potential novel methylation reagents through a systematic investigation of the thermodynamics and reactivity of methylsubstituted organic hydride radical cations (XH •+ s). In this work, 45 classical and important XH •+ s were designed to investigate the relationship between their structure and reactivity, to find excellent or potential methylation reagents. The Gibbs free energy and activation free energy of XH •+ to release the methyl radical in MeCN at 298.15 and 355 K are calculated with the density functional theory (DFT) method to quantitatively measure the reactivity of XH •+ as a methylation reagent in this work. The relationships between structures and reactivities on XH •+ s as methylation reagents are well examined. Since we have calculated the Gibbs free energy and activation free energy of trifluoromethylsubstituted organic hydride compound radical cations (X′H •+ ) releasing trifluoromethyl radicals in MeCN with the DFT method in our previous work, accordingly, the relationship of thermodynamics and reactivity between X′H •+ releasing trifluoromethyl radical and XH •+ releasing methyl radical is discussed in detail. Excitingly, 4 XH •+ s (1H •+ , 3H •+ ∼4H •+ , and 44H •+ ) are found to be excellent methyl radical reagents, while 9 XH •+ s (5H

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“…On the basis of experiment results and literature reports, ,,,− , a plausible reaction mechanism was proposed (Scheme ). First, oxidative addition of Pd(0) catalyst with the in situ formed mixed anhydride I to afford intermediate II , which then underwent decarbonylation and subsequent alkyne insertion with internal alkyne 2 to generate the alkenyl palladium intermediate IV .…”

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confidence: 98%

“…Carboxylic acids are readily available, stable and nontoxic raw chemicals that have been widely applied in organic synthesis. , In recent years, transition metal-catalyzed decarbonylative couplings of carboxylic acids have attracted much attention because of the redox-neutral reaction conditions and high efficiency in generating electrophilic synthons that differ from the well-developed decarboxylative couplings, thus offering a good complementary to the efficient conversion of carboxylic acids. , Among the many developed transformations, decarbonylative coupling of carboxylic acids with C–H species to build C–C bonds is very attractive for its direct C–H functionalization under oxidant free conditions, which has the advantages of low reaction costs, safe operation, and also better tolerance to reductive functional groups for substrates. In 2013, a novel Rh-catalyzed cross-coupling between aryl carboxylic acids with arenes through the decarbonylation of the acid and direct C–H bond activation was first reported by Shi and Sun .…”

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confidence: 99%