A brief historical overview of organometallic chemistry in organic synthesis: From the 19th to the 20th century

Abstract

Organometallic reagents and catalysts have now assumed an integral role in contemporary organic synthesis. However, the intellectual progression from early stoichiometric reagents to advanced catalytic systems is rarely presented in a manner accessible to newcomers in the field. While standard textbooks and specialized reviews offer comprehensive descriptions of organometallic bonding and individual transformations, they often either assume significant prior knowledge or examine each development in isolation, without elucidating the mechanistic connections that span over a century of advancements. This review aims to provide a brief historical overview of this progression, beginning with the discovery of Zeise's salt and the development of organometallic reagents of the 19th century and extending through the rise of homogeneous catalysis, asymmetric hydrogenation, cross‐coupling, and olefin metathesis, and ending with the emergence of C–H bond activation in the 20th century. Throughout, the focus remains on the underlying mechanistic principles that propelled each breakthrough and the new synthetic opportunities they facilitated.