ortho-C-O arylation of aromatic amides with Grignard reagents through the Meyers reaction

Ya Wu1,2, Bohao Wang1,2, Yiran Shi1

  • 1School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an 710072, China. liupei@nwpu.edu.cn.

PubMed

Related Concept Videos

Preparation of Carboxylic Acids: Carboxylation of Grignard Reagents01:13

Preparation of Carboxylic Acids: Carboxylation of Grignard Reagents

Carboxylic acids can be prepared by the carboxylation of Grignard reagents (RMgX). This method is convenient for converting alkyl (primary, secondary or tertiary), vinyl, benzyl, and aryl halides to carboxylic acids with one additional carbon than the starting RMgX.
5.9K
Acid Halides to Alcohols: Grignard Reaction01:15

Acid Halides to Alcohols: Grignard Reaction

Organomagnesium halides, commonly known as Grignard reagents, convert acid halides to tertiary alcohols. The reaction requires two equivalents of the Grignard reagent and proceeds via a ketone intermediate.
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
2.9K
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism01:26

Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism

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...
4.0K
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview01:07

Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview

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
Amines to Amides: Acylation of Amines01:19

Amines to Amides: Acylation of Amines

Various carboxylic acid derivatives (such as acid chlorides, esters, and anhydrides) can be used for the acylation of amines to yield amides. The reaction requires two equivalents of amines. The first amine molecule functions as a nucleophile and attacks the carbonyl carbon to produce a tetrahedral intermediate. This is followed by the loss of the leaving group and restoration of the C=O bond.
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
3.4K
Alcohols from Carbonyl Compounds: Grignard Reaction02:00

Alcohols from Carbonyl Compounds: Grignard Reaction

Grignard reagents are one of the most commonly used reagents used to synthesize alcohols from carbonyl compounds. Grignard reagents are organomagnesium halides with a highly polar carbon–magnesium bond. Due to the partial ionic nature of the C–Mg bond, the carbon functions as a strong nucleophile and attacks electrophiles like carbonyl carbon.
Magnesium from the reagent coordinates with carbonyl oxygen, further reducing the carbonyl carbon's electron density. Thus, the...
6.8K