Related Experiment Video
Updated: Oct 13, 2025
10:57
Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
18.5K
Electrochemical Reductive N-Methylation with CO2 Enabled by a Molecular Catalyst
Conor L Rooney1,2, Yueshen Wu1,2, Zixu Tao1,2
1Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Journal of the American Chemical Society
|November 16, 2021
Summary
This study introduces the first electrochemical reductive N-methylation using carbon dioxide (CO2) as a sustainable one-carbon source. The novel method efficiently converts amines and nitro-compounds into N-methylamines, advancing green chemistry.
Area of Science:
- Green Chemistry
- Electrocatalysis
- Organic Synthesis
Background:
- Sustainable chemical industry requires benign methylation using carbon dioxide (CO2).
- Electrochemical CO2 reduction is studied, but reductive methylation is unexplored in electrocatalysis.
Purpose of the Study:
- Report the first electrochemical reductive N-methylation reaction using CO2.
- Demonstrate compatibility with various nitrogenous compounds and develop a cascade process for nitro-compounds.
Main Methods:
- Utilized cobalt phthalocyanine catalyst on carbon nanotubes for N-methylation.
- Investigated reaction mechanism involving electrophilic carbon intermediate (formaldehyde) and nucleophilic reactants.
- Developed a cascade reduction process for concurrent reduction of CO2 and nitro-compounds.
Main Results:
- Successfully achieved electrochemical reductive N-methylation of amines, hydroxylamines, and hydrazine with CO2.
- Identified amine nucleophilicity as a key factor for C-N coupling efficacy.
- Developed a cascade process yielding N-methylamines from nitro-compounds with high monomethylation selectivity.
Conclusions:
- Established the first electrocatalytic reductive N-methylation using CO2.
- Demonstrated a versatile and sustainable method for synthesizing N-methylamines from diverse nitrogenous feedstocks, including nitro-compounds.
Related Concept Videos
02:23Alcohols from Carbonyl Compounds: Reduction
11.2K
Reduction is a simple strategy to convert a carbonyl group to a hydroxyl group. The three major pathways to reduce carbonyls to alcohols are catalytic hydrogenation, hydride reduction, and borane reduction.
Catalytic hydrogenation is similar to the reduction of an alkene or alkyne by adding H2 across the pi bond in the presence of transition metal catalysts like Raney Ni, Pd–C, Pt, or Ru. Aldehydes and ketones can be reduced by this method, often under mild to moderate heat (25–100°C) and...
Catalytic hydrogenation is similar to the reduction of an alkene or alkyne by adding H2 across the pi bond in the presence of transition metal catalysts like Raney Ni, Pd–C, Pt, or Ru. Aldehydes and ketones can be reduced by this method, often under mild to moderate heat (25–100°C) and...
11.2K
01:17Phase II Reactions: Methylation Reactions
409
Methylation is a phase II biotransformation process involving the attachment of a methyl group to a substrate. Enzymes known as methyltransferases orchestrate this reaction.
The mechanism of methylation unfolds in two stages. The first stage sees a methyltransferase enzyme facilitating the transfer of a methyl group from S-adenosylmethionine (SAM) to the substrate, forming S-adenosylhomocysteine (SAH). The second stage involves further metabolism of SAH into homocysteine, which can be recycled...
The mechanism of methylation unfolds in two stages. The first stage sees a methyltransferase enzyme facilitating the transfer of a methyl group from S-adenosylmethionine (SAM) to the substrate, forming S-adenosylhomocysteine (SAH). The second stage involves further metabolism of SAH into homocysteine, which can be recycled...
409
01:19Oxidation and Reduction of Organic Molecules
8.2K
Energy production within a cell involves many coordinated chemical pathways. Most of these pathways are combinations of oxidation and reduction reactions, which occur at the same time. An oxidation reaction strips an electron from an atom in a compound, and the addition of this electron to another compound is a reduction reaction. Because oxidation and reduction usually occur together, these pairs of reactions are called redox reactions.
The removal of an electron from a molecule, results in a...
The removal of an electron from a molecule, results in a...
8.2K
00:55Nitriles to Amines: LiAlH4 Reduction
3.9K
Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
3.9K
01:38Preparation of Amines: Reductive Amination of Aldehydes and Ketones
3.2K
Carbonyl compounds and primary amines undergo reductive amination first to produce imines, followed by secondary amines in the same reaction mixture, using selective reducing agents like sodium cyanoborohydride or sodium triacetoxyborohydride. Reductive amination produces different degrees of substitution of amines depending on the starting amine substrate.
3.2K
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.5K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.5K