Related Experiment Video
Updated: Apr 9, 2026
A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Kumada-Grignard-type biaryl couplings on water
Anish Bhattacharjya1, Piyatida Klumphu1, Bruce H Lipshutz1
1Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
This study demonstrates a novel Kumada-like coupling reaction in water, forming biaryls from aromatic halides using palladium catalysis and magnesium metal. This method bypasses the need for preformed Grignard reagents, offering a greener alternative.
Area of Science:
- Organic Chemistry
- Catalysis
- Green Chemistry
Background:
- Traditional Kumada cross-couplings require preformed Grignard reagents and anhydrous conditions.
- Palladium catalysis is widely used for cross-coupling reactions.
Purpose of the Study:
- To investigate a novel Kumada-like cross-coupling reaction in an aqueous medium.
- To explore the formation of biaryls from aromatic halides using palladium and magnesium in water.
Main Methods:
- Reaction of aromatic halides with excess magnesium metal in pure water.
- Catalysis using palladium(II) species.
- Analysis of reaction products for biaryl formation.
Main Results:
- Successful synthesis of symmetrical and unsymmetrical biaryls.
- Indication of a net Kumada-like biaryl coupling occurring in situ.
- Evidence suggesting the involvement of Grignard reagents formed in situ in water.
Conclusions:
- A novel, water-based Kumada-like coupling reaction has been developed.
- The reaction proceeds efficiently in pure water, offering a potentially greener synthetic route.
- In situ Grignard reagent formation in water is proposed as the likely mechanism.
More Related Videos
05:34Efficient Synthesis of Polyfunctionalized Benzenes in Water via Persulfate-promoted Benzannulation of α,β-Unsaturated Compounds and Alkynes
Published on: December 16, 2019
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
11:44Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Related Concept Videos
01:15Acid Halides to Alcohols: Grignard Reaction
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,...
01:08Esters to Alcohols: Grignard Reaction
The reaction requires two equivalents of the Grignard reagent and introduces two identical alkyl groups, derived from the Grignard reagent, bonded to the hydroxyl-bearing carbon of the alcohol.
The reaction follows the typical nucleophilic acyl substitution mechanism. The Grignard...
01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
02:15Preparation of Alcohols via Addition Reactions
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
01:13Preparation of Carboxylic Acids: Carboxylation of Grignard Reagents
01:20Aldehydes and Ketones with Water: Hydrate Formation
The formation of hydrates is a reversible reaction. Hydrate formation is influenced by steric and electronic factors accompanying the alkyl substituents on the carbonyl group: The rate of hydrate formation increases with a decrease in the number of alkyl groups attached to the carbonyl carbon. Hence,...