Recent Advances in the Functionalization of Hydrocarbons: Synthesis of Amides and its Derivatives

Abstract

The functionalization of hydrocarbons represents an attractive approach for the synthesis of amides. The amide bond is one of the most fascinating functional groups in nature, owing to its high bond polarity, stability, and conformational diversity. Amides play an essential role in the composition of many natural products, agrochemicals, peptides, polymers, proteins, biologically active systems, and functional materials. The present review focuses on recent breakthroughs and current challenges for the functionaliza-tion of hydrocarbons to synthesize amides. This review provides comprehensive coverage on recent reports of various efficient metal-catalyzed and metal-free methods for the synthesis of amides from hydrocarbons (such as methylarenes, alkenes, and alkynes). We also show the reaction mechanisms of representative reactions in a detailed way with numerous examples and applications of these methods in the synthesis of bioactive compounds.

Synthesis, Characterization, and DFT Studies of N-(3,5-Bis(trifluoromethyl)benzyl)stearamide

“…The procedures most used in the pharmaceutical industry for amide synthesis involve the acylation reaction of activated carboxylic acid derivatives such as acyl chlorides, anhydrides, or esters with amines, as well as the direct amidation of carboxylic acids with amines employing stoichiometric quantities of diverse coupling reagents, which generate large quantities of waste leading to poor atom-economy and tricky purification procedures [20][21][22]. Hence, in the past two decades, there was a significant increase in the development of sustainable catalytic methods for amide bond formation under mild conditions with a broad synthetic scope [23][24][25][26]. In particular, we recently reported a solventless direct amidation of non-activated carboxylic acids with amines employing a biogenic CuO−CaCO 3 catalyst for amide synthesis in moderate to high yields under normal atmospheric conditions [27].…”

C–H Functionalization of Aromatic Amides

“…The steric effect of the group present on the substrate can be used with a variety of directing groups for the regioselective C–H functionalization of aromatic compounds, e.g., 8‐aminoquinoline, N,O ‐bidentate species, amide‐oxazoline, N ‐methoxy amide, oxalyl amide, etc. As an important and common chemical structure, amides are widely observed in various natural products, small drug molecules, organic synthesis intermediates and functional materials . In addition, amide groups represent a class of highly efficient directing groups commonly used for the selective functionalization of aromatic amides.…”

New Efficient Eco‐Friendly Supported Catalysts for the Synthesis of Amides with Antioxidant and Anti‐Inflammatory Properties

“…More than forty research articles have been dedicated this year only to the synthesis of amides. [8,9] Classical synthetic pathway to access amides include the use of activated carboxylic acid derivatives such as activated esters, acyl halides or anhydrides in the presence of various amounts of coupling agents, generally expensive and/or toxic. [8,10] Recent developments in amide synthesis using nonactivated starting materials have been described.…”

“…[8,9] Classical synthetic pathway to access amides include the use of activated carboxylic acid derivatives such as activated esters, acyl halides or anhydrides in the presence of various amounts of coupling agents, generally expensive and/or toxic. [8,10] Recent developments in amide synthesis using nonactivated starting materials have been described. [10] These environmentally friendly methodologies mainly include: i) direct amidation of carboxylic acids with amines mediated by different catalysts, the most employed being boric acid derivatives under heating, or under microwave irradiation; ii) transamidation between amides and amines in presence of transition metals catalysts (iron, nickel and manganese derivatives being the most used); iii) aminolysis reaction of esters with amines under different catalytic conditions (e. g. transition metals derivatives [11] ).…”

“…[18] The nucleophilic substitution reaction (7) between 2,4-dinitrophenyl cinnamate and ethanolamine in water containing 20 mol % of DMSO at 25°C was also reported to furnish idrocilamide without yield indication. [19] Another starting material used to provide idrocilamide was (E)-cinnamaldehyde as shown in pathway (8). [20] The reaction started by adding DBU to a solution of 1,3-dimethyltriazolium iodide and ethanolamine in THF under argon atmosphere (8-xii).…”