Synthesis of Borylated Compounds Through Decarboxylative and Decarbonylative Reactions

Organoboronates and organoboronic acids are important and versatile building blocks in organic synthesis, in materials science, and in medicinal chemistry as carboxylic acid bioisosteres. The most employed reactions to generate organoboronates are transmetallation and hydroboration of olefins. However, as carboxylic acids are commercially available, naturally abundant, structurally diverse, and bench‐stable, their direct transformation into boronate esters or boronic acids is very attractive. This review highlights the recent developments in the direct decarboxylative, decarbonylative borylations, and alkylations of carboxylic acid derivatives. This review intends to be a practical tool for selection of suitable reaction conditions for specific transformations. The parameters facilitating the decarboxylation process are highlighted as a function of the substrate structure. The reviewed methodologies span from transition‐metal catalysis to photocatalysis.