Litcius/Paper detail

Ester dance reaction on the aromatic ring

Kaoru Matsushita, Ryosuke Takise, Kei Muto, Junichiro Yamaguchi

2020Science Advances44 citationsDOIOpen Access PDF

Abstract

Aromatic rearrangement reactions are useful tools in the organic chemist's toolbox when generating uncommon substitution patterns. However, it is difficult to precisely translocate a functional group in (hetero) arene systems, with the exception of halogen atoms in a halogen dance reaction. Here, we describe an unprecedented "ester dance" reaction: a predictable translocation of an ester group from one carbon atom to another on an aromatic ring. Specifically, a phenyl carboxylate substituent can be shifted from one carbon to an adjacent carbon on a (hetero) aromatic ring under palladium catalysis to often give a thermodynamically favored, regioisomeric product with modest to good conversions. The obtained ester moiety can be further converted to various aromatic derivatives through the use of classic and state-of-the-art transformations including amidation, acylations, and decarbonylative couplings.

Topics & Concepts

Ring (chemistry)SubstituentChemistryHalogenElectrophilic aromatic substitutionMoietyAromaticityCatalysisCarboxylateCarbon fibersMedicinal chemistryOrganic chemistryMoleculeAlkylMaterials scienceComposite materialComposite numberCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsAdvanced Synthetic Organic Chemistry