Recent Advances in the Metal-Catalyzed Activation of Amide Bonds.

  title={Recent Advances in the Metal-Catalyzed Activation of Amide Bonds.},
  author={Moreshwar Bhagwan Chaudhari and Boopathy Gnanaprakasam},
  journal={Chemistry, an Asian journal},
  volume={14 1},
The amide functional group is commonly found in peptides, proteins, pharmaceutical compounds, natural products, and polymers. The synthesis of amides is typically performed by using classical approaches that involve the reaction between a carboxylic acid and an amine in the presence of an activator. Amides are thought to be an inert functional group, because they are unsusceptible to nucleophile attack, owing to their low electrophilicity. The reason for this resistance is clear: the resonance… 
Recent developments in catalytic amide bond formation
Amide bond forming reactions are critical for both polypeptide synthesis and medicinal chemistry. Most current approaches for amidation employ stoichiometric activating agents, but such methods are
Transamidation and Decarbonylation of N-Phthaloyl-Amino Acid Amides Enabled by Palladium-Catalyzed Selective C-N Bond Cleavage.
An efficient Pd-catalyzed transamidation and decarbonylation of multiamide structure molecules through C-N bond cleavage with excellent chemoselectivity is described.
Selective C-C bond cleavage of amides fused to 8-aminoquinoline controlled by a catalyst and an oxidant.
Copper-catalyzed direct C-C bond cleavage of amides fused to 8-aminoquinoline as a directing group to form urea in the presence of amines and dioxygen is reported, providing access to cyclohexanone.
Hydrogen-bond-assisted transition-metal-free catalytic transformation of amides to esters
The amide C-N cleavage has drawn a broad interest in synthetic chemistry, biological process and pharmaceutical industry. Transition-metal, luxury ligand or excess base were always vital to the
N-Ethynylation of Anilides Decreases the Double-Bond Character of Amide Bond while Retaining trans-Conformation and Planarity.
N-Ethynyl-substituted acetanilides undergo selective C(O)-N bond or N-C(sp) bond cleavage reactions and have potential applications as activated amides for coupling reactions or easily cleavable tethers.
Site-selective Amide Functionalization by Catalytic Azoline Engrafting
An artificial cyclodehy-dratase is designed, a catalytic system for site-selective modification of peptides and natural products by engrafting heterocyclic into their scaffolds by integrating molybdenum(VI) center that was decorated with a sterically congest-ed tripod ligand and the utility of the new protocol is demonstrated in direct conversion into amines and thioamides.
Evaluation of Cyclic Amides as Activating Groups in N-C Bond Cross-Coupling: Discovery of N-Acyl-δ-valerolactams as Effective Twisted Amide Precursors for Cross-Coupling Reactions.
A comparative evaluation of a series of cyclic amides as activating groups in amide N-C(O) bond cross-coupling reveals N-acyl-δ-valerolactams as a highly effective class of mono-N-ACYl-activated amide precursors in cross- coupling.
Nickel-Catalyzed Deaminative Acylation of Activated Aliphatic Amines with Aromatic Amides via C-N Bond Activation.
A Ni-catalyzed reductive deaminative cross-electrophile coupling reaction between Katritzky salts and aromatic amides is described, expected to be useful for late-stage functionalization of complex compounds.
Synthesis of biaryl ketones by arylation of Weinreb amides with functionalized Grignard reagents under thermodynamic control vs. kinetic control of N,N-Boc2-amides.
A highly efficient method for chemoselective synthesis of biaryl ketones by arylation of Weinreb amides with functionalized Grignard reagents, which offers a major advantage over the recently established cross-coupling of amides by oxidative addition of N-C(O) bonds.


Conversion of Amides to Esters by the Nickel-Catalyzed Activation of Amide C–N Bonds
It is demonstrated that amide carbon–nitrogen bonds can be activated and cleaved using nickel catalysts and is expected to lead to the further use of amides in the construction of carbon–heteroatom or carbon–carbon bonds using non-precious-metal catalysis.
Nickel-Catalyzed Esterification of Aliphatic Amides.
Recent studies have demonstrated that amides can be used in nickel-catalyzed reactions that lead to cleavage of the amide C-N bond, with formation of a C-C or C-heteroatom bond. However, the general
Twisted Amides: From Obscurity to Broadly Useful Transition-Metal-Catalyzed Reactions by N-C Amide Bond Activation.
A detailed overview of the prominent role of amide bond destabilization as a driving force in the development of transition-metal-catalyzed cross-coupling reactions by N-C bond activation is presented.
Breaking Amides using Nickel Catalysis.
Ni catalysis provides exciting new tools to build C-heteroatom and C-C bonds using an unconventional reactant (i.e., the amide), which is ideally suited for use in multi-step synthesis.
Highly selective transition-metal-free transamidation of amides and amidation of esters at room temperature
The authors show a general and operationally-simple protocol for the transamidation of amides and amidation of esters by highly selective acyl cleavage with non-nucleophilic amines under mild conditions.
Transamidation of N-acyl-glutarimides with amines.
The development of new transamidation reactions for the synthesis of amides is an important and active area of research due to the central role of amide linkage in various fields of chemistry.
Resonance Destabilization in N-Acylanilines (Anilides): Electronically-Activated Planar Amides of Relevance in N-C(O) Cross-Coupling.
It is demonstrated that amide nN → π*C═O resonance in simple anilides can be varied by as much as 10 kcal/mol, which has important implications for the design of N-C(O) amide cross-coupling reactions and control of the molecular conformation of anilide by resonance effects.
Nickel-catalysed Suzuki-Miyaura coupling of amides.
These studies demonstrate that amides, despite classically considered inert substrates, can be harnessed as synthons for use in reactions that form C-C bonds through cleavage of the C-N bond using non-precious metal catalysis.
Decarbonylative Phosphorylation of Amides by Palladium and Nickel Catalysis: The Hirao Cross-Coupling of Amide Derivatives.
A catalytic deamidative phosphorylation of a wide range of amides using a palladium or nickel catalyst giving aryl phosphonates in good to excellent yields is reported, constituting the first example of a transition-metal-catalyzed generation of C-P bonds from amides.
Decarbonylative cross-coupling of amides.
Recent advances and key developments in the field of decarbonylative cross-coupling reactions of amides are presented as well as future challenges and potential applications for this exciting field are discussed.