Related Experiment Video
Updated: Sep 10, 2025
06:00
One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates
Published on: January 15, 2018
7.6K
Rapid, Room-Temperature Amidation via Tandem Titanium Amido Complex and Titanium Carboxylate Intermediates
Henry J Hamann1, Madison J Snyder1, Aman G Singh1
1Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907, United States.
Organic Letters
|August 23, 2025
Summary
Titanium amido complexes react with carboxylic acids to form activated titanium carboxylates. These intermediates enable rapid amidation at room temperature, offering a new synthetic route.
Area of Science:
- Organometallic Chemistry
- Synthetic Organic Chemistry
Background:
- Titanium tetrachloride is a common precursor in organometallic synthesis.
- Amidation reactions are crucial for synthesizing amides, which are vital in pharmaceuticals and materials.
Purpose of the Study:
- To develop a novel, efficient method for synthesizing titanium carboxylates.
- To investigate the rapid amidation of activated titanium carboxylates at room temperature.
Main Methods:
- In situ generation of titanium amido complexes from titanium tetrachloride.
- Reaction of titanium amido complexes with various carboxylic acids.
- Characterization using spectroscopic studies and control reactions.
Main Results:
- Successfully generated activated titanium carboxylates.
- Achieved rapid amidation reactions at ambient temperatures.
- Spectroscopic data and control experiments confirmed the proposed reaction pathway.
Conclusions:
- The developed methodology provides a facile and rapid route for amidation.
- Activated titanium carboxylates are effective intermediates for amide synthesis.
- This approach holds significant synthetic potential for organic chemistry.
![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
Related Concept Videos
01:26Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
3.6K
The Hofmann and Curtius rearrangement reactions can be applied to synthesize primary amines from carboxylic acid derivatives such as amides and acyl azides. In the Hofmann rearrangement, a primary amide undergoes deprotonation in the presence of a base, followed by halogenation to generate an N-haloamide. A second proton abstraction produces a stabilized anionic species, which rearranges to an isocyanate intermediate via an alkyl group migration from the carbonyl carbon to the neighboring...
3.6K
01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.9K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.9K
01:29Preparation of Amides
3.2K
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...
3.2K
01:07Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview
3.3K
In the presence of an aqueous base and a halogen, primary amides can lose the carbonyl (as carbon dioxide) and undergo rearrangement to form primary amines. This reaction, called the Hofmann rearrangement, can produce primary amines (aryl and alkyl) in high yields without contamination by secondary and tertiary amines.
3.3K
01:23Aldehydes and Ketones with Amines: Imine Formation Mechanism
6.4K
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...
6.4K
00:53Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
2.0K
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
2.0K