Aromatic amines from carboxylic acids and ammonia. A homogeneous catalytic process

Arzoumanidis, Gregory G.; Rauch, Frank C.

doi:10.1021/jo00332a042

Cited by 16 publications

(6 citation statements)

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“…An early report on the amination of benzoic acid was disclosed by Arzoumanidis and Rauch in 1973 . They showed that the reaction of copper benzoates with ammonia at a high temperature and pressure provides aniline with concominant decarboxylation.…”

Section: C(sp2)–h Functionalizationmentioning

confidence: 99%

Recent Advances in External-Directing-Group-Free C–H Functionalization of Carboxylic Acids without Decarboxylation

et al. 2021

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The selective functionalization of C–H bonds is an extremely important topic in present-day organic synthesis, as it utilizes the most abundant portion of a molecule as a tool for synthetic manipulations. Despite the great progress over the past decade, the major limitation remains the use of an equivalent amount of a directing group to generate the product. The utilization of a native carboxylate group for the same purpose has come up as a better alternative to perform C–H activation, as no exogenous directing group is required to perform the reaction. In this Perspective, we intend to provide a broader picture of transformations that have been carried out by assistance from the carboxylate group and could be applied routinely in the synthesis of complex molecules. The intact carboxylic group in the substrate could be further transformed into different functional moieties, which increases the diversity of such reactions. Extensive coverage of the topic of carboxylate-aided functionalizations of organic molecules without decarboxylation is expected to make this Perspective unique and extremely beneficial to researchers in academia and industry.

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Section: C(sp2)–h Functionalizationmentioning

confidence: 99%

Recent Advances in External-Directing-Group-Free C–H Functionalization of Carboxylic Acids without Decarboxylation

et al. 2021

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“…It was then reported that Cu II benzoates react with ammonia at high pressures and temperatures to give anilines with concomitant protodecarboxylation. However, Arzoumanidis and Rauch later highlighted the limitations of this catalytic methodology, namely low yields coupled with the formation of multiple products and the necessity to use harsh conditions (Scheme ) . These two reports nonetheless remain the only examples of the use of a carboxylic acid as a traceless directing group for C−N bond formation.…”

Section: C−n Bond Formationmentioning

confidence: 99%

“…Moreover, the synthesis of diarylamine derivatives of anthranilic acids is unknown via this carboxylate‐directed strategy and access to N ‐alkyl anthranilic acids was provided only through the use of cyclic chloramines. Finally, although the formation of an ortho C−N bond theoretically allows an efficient concomitant decarboxylative pathway, this feat has to date only been achieved by Arzoumanidis and Rauch and led to mixtures of compounds that are difficult to separate.…”

Section: C−n Bond Formationmentioning

confidence: 99%

Carboxylic Acids as Directing Groups for C−H Bond Functionalization

Drapeau

Gooßen

2016

Chemistry A European J

269

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The selective transformation of C-H bonds is one of the most desirable approaches to creating complexity from simple building blocks. Several directing groups are efficient in controlling the regioselectivity of catalytic C-H bond functionalizations. Among them, carboxylic acids are particularly advantageous, since they are widely available in great structural diversity and at low cost. The carboxylate directing groups can be tracelessly cleaved or may serve as the anchor point for further functionalization through decarboxylative couplings. This Minireview summarizes the substantial progress made in the last few years in the development of reactions in which carboxylate groups direct C-H bond functionalizations with formation of C-C, C-O, C-N, or C-halogen bonds at specific positions. It is divided into sections on C-C, C-O, C-N, and C-halogen bond formation, each of which is subdivided by reactions and product classes. Particular emphasis is placed on methods that enable multiple derivatizations by combining carboxylate-directed C-H functionalization with decarboxylative couplings.

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“…20,21 Known methods for the aromatic decarboxylative functionalization usually require either specialized substrates (i.e., ortho-substituted benzoic acids) 22 or very high temperature. 23,24 Although the Dow phenol process has been well investigated, its reaction conditions are harsh (240− 280 °C) and the yield is very low with a limited scope. Moreover, the newly introduced −OH group in Dow's process is at the ortho position instead of the ipso-substitution of −CO 2 H. 25 In 2021, the Ritter group reported a coppermediated decarboxylative esterification protocol promoted by purple light at mild temperature (35 °C).…”

Section: ■ Introductionmentioning

confidence: 99%

Simple and Practical Conversion of Benzoic Acids to Phenols at Room Temperature

2022

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Phenols are important organic molecules because they have found widespread applications in many fields. Herein, an efficient and practical approach to prepare phenols from benzoic acids via simple organic reagents at room temperature is reported. This approach is compatible with various functional groups and heterocycles and can be easily scaled up. To demonstrate its synthetic utility, bioactive molecules and unsymmetrical hexaarylbenzenes have been prepared by leveraging this transformation as strategic steps. Mechanistic investigations suggest that the key migration step involves a free carbocation instead of a radical intermediate. Considering the abundance of benzoic acids and the utility of phenols, it is anticipated that this method will find broad applications in organic synthesis.

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Aromatic amines from carboxylic acids and ammonia. A homogeneous catalytic process

Cited by 16 publications

References 0 publications

Recent Advances in External-Directing-Group-Free C–H Functionalization of Carboxylic Acids without Decarboxylation

Recent Advances in External-Directing-Group-Free C–H Functionalization of Carboxylic Acids without Decarboxylation

Carboxylic Acids as Directing Groups for C−H Bond Functionalization

Simple and Practical Conversion of Benzoic Acids to Phenols at Room Temperature

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