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Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Metal-catalysed approaches to amide bond formation
C Liana Allen1, Jonathan M J Williams
1Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
Chemical Society Reviews
|March 19, 2011
Summary
Metal catalysts offer efficient amide bond formation using various starting materials like acids, esters, aldehydes, and alcohols. Emerging methods utilize nitriles, oximes, and carbon monoxide for powerful synthetic strategies.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Amide bond formation is a fundamental transformation in organic synthesis.
- Traditional methods often require harsh conditions or stoichiometric reagents.
- Metal-catalyzed reactions offer milder and more efficient alternatives.
Purpose of the Study:
- To review recent advancements in metal-catalyzed amide bond formation.
- To highlight diverse starting materials and catalytic systems.
- To showcase emerging and powerful methodologies.
Main Methods:
- Review of literature on metal-catalyzed amide bond formation.
- Coupling reactions involving acids, esters, aldehydes, and alcohols with amines.
- Oxidative couplings and reactions utilizing nitriles, oximes, and carbon monoxide.
Main Results:
- Demonstrated utility of various metal catalysts (e.g., palladium, copper) in amide synthesis.
- Successful amide formation from diverse precursors including acids, esters, aldehydes, alcohols, nitriles, and oximes.
- Highlighting carbon monoxide as a key C1 source in transition metal-catalyzed couplings.
Conclusions:
- Metal catalysis provides versatile and efficient routes for amide bond construction.
- Diverse substrates and catalytic systems are continually expanding the scope of amide synthesis.
- Emerging techniques offer powerful tools for accessing amides, crucial in various chemical fields.
Related Concept Videos
01:29Preparation of Amides
Amides are synthesized by treating carboxylic acids with amines in the presence of dehydrating agents like dicyclohexylcarbodiimide (DCC).
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
01:16Aldehydes and Ketones with Amines: Imine and Enamine Formation Overview
Primary amines react with carbonyl compounds—aldehydes and ketones—to generate imines. Imines consist of a C=N double bond and are named Schiff bases after its discoverer—the German chemist Hugo Schiff. On the other hand, secondary amines react with carbonyl compounds to give enamines. In enamines, the presence of a C=C double bond adjacent to the nitrogen atom leads to the delocalization of the lone pair.
01:23Aldehydes and Ketones with Amines: Imine Formation Mechanism
Imine formation involves the addition of carbonyl compounds to a primary amine. It begins with the generation of carbinolamine through a series of steps involving an initial nucleophilic attack and then several proton transfer reactions. The second part includes the elimination of water, as a leaving group, to give the imine.
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
01:22Preparation of 1° Amines: Azide Synthesis
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
01:14Aldehydes and Ketones with Amines: Enamine Formation Mechanism
Enamine formation involves the addition of carbonyl compounds to a secondary amine through a series of reactions. The mechanism begins with the generation of carbinolamine, a nucleophilic attack followed by several proton transfer reactions. The hydroxyl group of the carbinolamine is converted into water to make a better leaving group that can push the reaction forward by eliminating a water molecule. In enamine formation, the last step involves the abstraction of a proton from the α carbon to...
01:07Acid Halides to Amides: Aminolysis
Aminolysis is a nucleophilic acyl substitution reaction, where ammonia or amines act as nucleophiles to give the substitution product. Acid halides react with ammonia, primary amines, and secondary amines to yield primary, secondary, and tertiary amides, respectively.
In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride...
In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride...