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Diazonium Group Substitution: –OH and –H01:19

Diazonium Group Substitution: –OH and –H

3.2K
Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
3.2K
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN101:14

Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1

2.6K
Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
2.6K
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions01:20

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

2.4K
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
2.4K
Acid Halides to Amides: Aminolysis01:07

Acid Halides to Amides: Aminolysis

4.1K
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...
4.1K
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview01:07

Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview

3.6K
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.
3.6K
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)01:30

Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)

4.6K
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
4.6K

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Copper-Catalyzed <i>trans</i>-Selective Aryl-Allylation of Ynamide: An Unconventional Route to Skipped Dienes.

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Regioselective Hydroarylation of Ynamides: A Direct Synthetic Route to Trisubstituted Enamides.

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Desymmetrization and Atroposelective Cobalt Catalyzed C-H Annulation of Phosphinic Amides with Ynamides.

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Direct β-C(sp<sup>3</sup>)-H Functionalization to Carbonyls: A Route to Aldehydic Acid Derivatives.

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Updated: Jan 8, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
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A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species

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Umpolung Strategy for Ynamide Difunctionalization.

Pragati Biswal1, Manoj Sethi1, Akhila K Sahoo1

  • 1School of Chemistry, University of Hyderabad, Hyderabad, Telangana, India.

Chemistry, an Asian Journal
|December 16, 2025
PubMed
Summary
This summary is machine-generated.

Tetrasubstituted enamides are synthesized via ynamide difunctionalization. This review explores umpolung strategies, reversing polarity for novel synthetic routes to these valuable compounds.

Keywords:
difunctionalizationenamidetetrasubstituted alkeneumpolungynamide

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Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry

Background:

  • Tetrasubstituted enamides are key structural motifs in conjugated materials and bioactive molecules.
  • Ynamide difunctionalization provides an atom-economical synthesis route for these frameworks.
  • Conventional ynamide additions follow predictable regioselectivity based on inherent electronic polarization.

Purpose of the Study:

  • To review recent advances in ynamide difunctionalization.
  • To highlight the application of umpolung strategies in ynamide chemistry.
  • To expand synthetic access to challenging molecular architectures.

Main Methods:

  • Difunctionalization of electron-rich ynamides.
  • Application of umpolung reactivity to reverse native polarity.
  • Exploration of novel bond-forming patterns.

Main Results:

  • Umpolung strategies enable new reactivity patterns in ynamide difunctionalization.
  • Access to diverse tetrasubstituted enamide structures is achieved.
  • Overcoming limitations of conventional regioselective additions.

Conclusions:

  • Umpolung strategies significantly expand the synthetic utility of ynamides.
  • This approach facilitates the construction of complex molecular frameworks.
  • Advances in ynamide chemistry offer new avenues for materials and medicinal chemistry.