Catalytic a-Arylation of Alkyl Alkanoates

α-Aryl carboxylic esters are important motifs or precursors in a wide variety of drugs, bioactive natural products, and pharmacologically active compounds. This chapter is an update to enrich the original Science of Synthesis chapter dedicated to the synthesis of alkyl alkanoates “Synthesis with Retention of the Functional Group” (Section 20.5.1.7). The current review focuses on recent advances in the catalytic α-arylation of alkyl alkanoates, and describes methods for the synthesis of α-aryl carboxylic compounds reported in the period 2001–2022. Seven main approaches are introduced: α-arylations of alkyl esters or their enolates, α-arylations of Reformatsky reagents with aryl halides, α-arylations of silyl ketene acetals, α-arylations of α-halo esters, α-arylations of α-diazo esters, decarboxylative or deacetylative α-arylation of β-carbonyl esters, and reductive C—O bond arylation of oxalates derived from α-hydroxy esters.