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Ester dance moves substituents around arene rings

Palladium catalyst offers unusual route to high-value compounds

by Mark Peplow, special to C&EN
July 13, 2020 | A version of this story appeared in Volume 98, Issue 27


An ester dance reaction.

Rearrangement reactions are useful ways to make substituted aromatic molecules, but most of the methods that shift a substituent around an arene ring leave a functional group behind at the vacated carbon. A rare exception is the “halogen dance” reaction, in which a halogen atom hops to a neighboring carbon, while a hydrogen atom takes its original place.

Junichiro Yamaguchi and a team of chemical choreographers at Waseda University have now developed an analogous “ester dance” reaction, the first carbonyl group rearrangement of its kind (Sci. Adv. 2020, DOI: 10.1126/sciadv.aba7614). The reaction uses a palladium catalyst with a diphosphine-thiophene ligand and a base, and works on more than 30 different arenes, including naphthalenes (example shown) and pyridines. The discovery was a happy accident. “I’ve never seen such a reaction before,” says Yamaguchi.

The researchers think the palladium catalyst inserts itself into the ester before forming a palladium-arene intermediate. This subsequently reforms the ester at a thermodynamically favored position on an adjacent carbon.

They also teamed the ester dance with a decarbonylative coupling reaction, offering a one-pot route to a range of high-value molecules. Yamaguchi says the dance could be used to create ester and carboxylic acid intermediates for pharmaceuticals and agrochemicals.


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