Copper Joins the Monoelectronic Game: Leveraging the Cu I Potential for SET‐, XAT‐, and HAT‐Driven Catalytic Organic Synthesis

ABSTRACT The growing interest in sustainable organic synthesis using catalysts based on first‐row transition metals has highlighted their remarkable ability to participate in monoelectronic processes. These processes have become a complement to the traditional two‐electron chemistry associated with transition metals. Recognizing their novelty and transformative potential, we aim to analyze and emphasize the role of copper(I)‐based catalysts in building molecular complexity from simple feedstocks by leveraging strategies that involve electron, halogen, and hydrogen transfer processes (SET, XAT, and HAT, respectively). Here, we provide a practical overview of the field by examining the main reactivity trends and key factors for achieving efficient transformations, while also showcasing the current versatility and synthetic utility of these methodologies.