A Straightforward Metal‐Free and Mild Base Promoted Amidation and Transesterification <i>via</i> Acyl C‐O bond Cleavage‐An Expedite Synthesis of Aromatic Amides and Esters

Karthik, S.; Sreedharan, Ramdas; Gandhi, Thirumanavelan

doi:10.1002/slct.201803105

Cited by 15 publications

(7 citation statements)

References 62 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thus, synthetic chemists look out for new methods that are relatively milder and easily accessible. Our group have previously reported the utilization of activated esters as an acyl electrophile in amidation and transesterification, [22a] and simple methyl and phenyl esters in acylation of carbon nucleophile ‐ oxindoles [22b] . In continuation of our group's long‐standing interest, herein we disclose the utility of simple methyl esters as an acyl electrophile ( i. e ., methyl ester as acyl electrophiles are scarce) to form unsymmetrical ketones by reacting with toluene.…”

Section: Introductionmentioning

confidence: 81%

Synthesis of α‐Aryl Ketones by Harnessing the Non‐Innocence of Toluene and its Derivatives: Enhancing the Acidity of Methyl Arenes by a Brønsted Base and their Mechanistic Aspects

et al. 2022

Self Cite

View full text Add to dashboard Cite

Ketones are the key functional group that recurs in chemistry and biology, and accessing them through simple and economic ways is highly desirable. Herein, we report the synthesis of unsymmetrical ketones from abundant toluene and alkyl esters, where volatile alcohols are the sole byproduct. This protocol applies to a repertoire of substrates bearing electron-donating, electron-withdrawing, and neutral substituents. Most importantly, the organometallic ferrocenyl ester underwent aroylation with ease. This method is the first example to furnish diketones from methyl arenes and diesters. Furthermore, cyclic imide was synthesized by this protocol utilizing KN(SiMe 3 ) 2 as a 'nitrogen' source. Density functional theory studies provide insight into deprotonation of toluene by K + -π interaction by increasing its acidity, and this being the rate-determining step.

show abstract

Section: Introductionmentioning

confidence: 81%

Synthesis of α‐Aryl Ketones by Harnessing the Non‐Innocence of Toluene and its Derivatives: Enhancing the Acidity of Methyl Arenes by a Brønsted Base and their Mechanistic Aspects

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…Unfortunately, such protocols result in the production of alcohol as a by-product, as exemplified in the work of Gandhi and co-workers (Figure 17a). [87] However, there exists a more promising alternative, which involves using low molecular weight alcohols as activation agents and leaving groups, as demonstrated in a recent study by McPherson et al [88] In this approach, trifluoroethanol (TFE) serves as the catalyst for the simple amidation of esters (Figure 17b). Nonetheless, it is regrettable that in this case, the reaction with secondary amines led to low yields.…”

Section: Making the Ro A Better Living Groupmentioning

confidence: 99%

Contemporary Approaches for Amide Bond Formation

Acosta‐Guzmán,

Ojeda‐Porras,

Gamba‐Sánchez

2023

Adv Synth Catal

View full text Add to dashboard Cite

Amide bond construction has garnered significant interest in recent decades due to amides being one of the most prevalent functional groups among bioactive molecules. Out of the thirty‐seven new drugs approved by the FDA in 2022, eleven are small molecules containing at least one amide bond. Additionally, there are nineteen large molecules approved as new drugs, some of which have peptide structures, and therefore, also bear amide bonds. In recent years, multiple teams have embraced the challenge of developing more efficient methods for amide bond formation. This dedication has led to numerous publications appearing monthly in prestigious journals, showcasing significant advancements in this field. The primary goal of this review is to present the most viable strategies for constructing the amide bond. It is crucial to differentiate between amide bond formation and amide synthesis; hence, the focus is on describing specific methods for forming new C(O)−N bonds. In particular, this review concentrates on the methods developed within the last six years. There is a particular emphasis on new approaches that consider the thought process when selecting the starting materials and functional groups. This approach ensures coverage of all the most common chemical transformations that yield new amide bonds.

show abstract

“…(Scheme 32). [67] Lately, our group demonstrated the synthesis of 3-alkylideneoxindoles 138 from acylation of oxindoles 136 with esters 137 as an acylating source via mixed Claisen condensation in the presence of LiHMDS and KOtBu. Notably, this reaction methodology is applicable to prepare biologically important Tenidap analogue.…”

Section: Estersmentioning

confidence: 99%

Alternative and Uncommon Acylating Agents – An Alive and Kicking Methodology

Sivaraj

Gandhi

2021

Chemistry An Asian Journal

Self Cite

View full text Add to dashboard Cite

Functionalizing and derivatising organic molecules is a centerpiece in organic synthesis. Succinctly manipulating and installing acyl moieties in organic molecules spurred the interest of chemists owing to its occurrence in natural products, bioactive molecules, pharmaceuticals, and advanced materials. Traditionally, access to acylation reaction was achieved by Friedel-Crafts reaction, Schotten-Baumann, and Vilsmeier-Haack acylation, however, these protocols own pitfalls. Further to make the acylation process attractive and environmentally friendly, toluene, aldehydes, alcohols, α-keto acids, amines, amides, esters, ethers, nitriles, alkynes, alkenes, ketenes, N-acylbenzotriazoles, ketones, thioacids, oximes, thiazolium carbinols, PIDA, diacyl disulfides and acyl salts were used as an acyl surrogates/reagents. Amusingly, these acylating reagents are considered uncommon and alternative to carboxylic acids, acid chlorides and acetic anhydrides. This short review aims to encompass the usage of acylating agents in transition-metal, metal-free, light-driven and other demanding conditions, and thus reveals their practicality.

show abstract

A Straightforward Metal‐Free and Mild Base Promoted Amidation and Transesterification via Acyl C‐O bond Cleavage‐An Expedite Synthesis of Aromatic Amides and Esters

Cited by 15 publications

References 62 publications

Synthesis of α‐Aryl Ketones by Harnessing the Non‐Innocence of Toluene and its Derivatives: Enhancing the Acidity of Methyl Arenes by a Brønsted Base and their Mechanistic Aspects

Synthesis of α‐Aryl Ketones by Harnessing the Non‐Innocence of Toluene and its Derivatives: Enhancing the Acidity of Methyl Arenes by a Brønsted Base and their Mechanistic Aspects

Contemporary Approaches for Amide Bond Formation

Alternative and Uncommon Acylating Agents – An Alive and Kicking Methodology

Contact Info

Product

Resources

About