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Green Boost For C–C Bond-Forming Reaction

Researchers expand aqueous organometallic chemistry by conducting a Barbier-Grignard-type direct arylation of carbonyls in water

by Stephen K. Ritter
June 30, 2014 | A version of this story appeared in Volume 92, Issue 26

Barbier-Grignard reactions were discovered more than a century ago, but with the advent of green chemistry, researchers are still considering ways to improve this useful set of organic synthesis methods. Feng Zhou and Chao-Jun Li of McGill University, in Montreal, have done so by developing a procedure for carrying out the first Barbier-Grignard direct arylation of carbonyls in water using unactivated aryl halides (Nat. Commun. 2014, DOI: 10.1038/ncomms5254). Barbier-Grignard chemistry normally involves using a metal to couple an alkyl halide with the carbonyl group of a partner to form an alcohol. Li’s group previously developed aqueous Barbier-Grignard reactions, but a carbonyl arylation with an unactivated aryl halide is unprecedented. In the new reaction, Zhou and Li coupled iodobenzenes with various aldehydes using zinc dust and a rhodium catalyst. The aqueous method bypasses several challenges encountered with conventional Barbier-Grignard reactions, such as strict exclusion of moisture and air and protection-deprotection of acidic hydrogens of the reactants. “The reaction thereby creates a safer, more convenient, and more environmentally benign strategy to access diarylmethanols and aryl alkyl alcohols, which are ubiquitous skeletons found in fine chemicals, biologically active molecules, and pharmaceuticals,” the researchers note.

A reaction scheme showing a Barbier-Grignard direct arylation through a rhodium catalyst,  zinc dust, and water.


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