Concept and Evolution of the Atherton-Todd Reaction

The pioneering work of Atherton and Todd on the coupling of dialkyl phosphites with primary amines in the presence of carbon tetrachloride evolved into one of the most powerful, elegant, and well-characterized methods for the direct synthesis of organophosphorus compounds, leading to the establishment of the now widely recognized Atherton-Todd reaction. Recent advancements have further demonstrated the broad applicability and synthetic potential of this methodology. This review provides an overview of the early developments and fundamental principles of the Atherton-Todd reaction, highlights recent progress in asymmetric catalytic versions, and discusses the mechanism of the reaction, which has been subject to some controversy in recent years. We hope that this review will stimulate further progress in this emerging field.