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ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3

6.0K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
6.0K
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN101:14

Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1

2.1K
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,...
2.1K
Diazonium Group Substitution: –OH and –H01:19

Diazonium Group Substitution: –OH and –H

2.8K
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.
2.8K
ortho–para-Directing Deactivators: Halogens01:24

ortho–para-Directing Deactivators: Halogens

5.5K
Halogens are ortho–para directors. They are more electronegative than carbon. Therefore, as ring substituents, they can withdraw electrons through the inductive effect and deactivate the aromatic ring towards electrophilic substitution. Halogens also have an electron-donating resonance effect on the ring, which influences the orientation of the incoming electrophile. If an electrophile attacks at the ortho or the para position, the halogen donates electrons and stabilizes the intermediate...
5.5K
Preparation of 1° Amines: Azide Synthesis01:22

Preparation of 1° Amines: Azide Synthesis

3.9K
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...
3.9K
Directing Effect of Substituents: ortho–para-Directing Groups01:14

Directing Effect of Substituents: ortho–para-Directing Groups

6.6K
Ortho–para directors are substituent groups attached to the benzene ring and direct the addition of an electrophile to the positions ortho or para to the substituent. All electron-donating groups are considered ortho–para directors. They donate electrons to the ring and make the ring more electron-rich. The ring is therefore susceptible to the addition of electrophiles. Substituents such as amino, hydroxy, or alkoxy, containing lone pairs on the atom adjacent to the ring, donate...
6.6K

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Updated: Jun 27, 2025

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
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A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis

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Rhodium-Catalyzed Direct ortho-Arylation of Anilines.

Clément Jacob1,2, Julien Annibaletto1, Ju Peng3

  • 1Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université libre de Bruxelles (ULB), Avenue F. D. Roosevelt 50, CP 160/06, 1050, Brussels, Belgium.

Angewandte Chemie (International Ed. in English)
|April 29, 2024
PubMed
Summary

A new rhodium-catalyzed direct ortho-arylation method uses aminophosphines as traceless directing groups for efficient aniline functionalization. This broadly applicable reaction offers high yields and regioselectivity for synthesizing complex ortho-arylated anilines.

Keywords:
C−H activationanilinesarylationrhodium catalysistraceless directing group

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Synthetic Methodology

Background:

  • Direct arylation of anilines is crucial for synthesizing valuable organic compounds.
  • Existing methods often suffer from limited scope, poor regioselectivity, or harsh conditions.

Purpose of the Study:

  • To develop an efficient and broadly applicable rhodium-catalyzed direct ortho-arylation of anilines.
  • To utilize readily available aminophosphines as traceless directing groups.
  • To achieve high yields, regioselectivity, and functional group tolerance.

Main Methods:

  • Rhodium-catalyzed direct ortho-arylation reaction.
  • Utilizing aminophosphines as directing groups and ligands.
  • Employing various (hetero)aryl iodides, bromides, and triflates.

Main Results:

  • Achieved high average yields of ortho-arylated anilines.
  • Demonstrated broad scope and excellent functional group compatibility.
  • Observed full regioselectivity with no competing diarylation.
  • Successfully used aryl bromides and triflates, and extended to diarylation.

Conclusions:

  • The developed method represents a significant advancement in aniline arylation.
  • Aminophosphines play a dual role as substrates and ligands in the rhodium catalysis.
  • This efficient protocol enables the synthesis of complex ortho-arylated anilines.