Thiourea‐Amine Catalysts: Innovation, Integration, and Sustainability

Thiourea‐based organocatalysts have emerged as a cornerstone in asymmetric synthesis, offering powerful activation modes via dual hydrogen bonding while operating under mild, metal‐free conditions. This review provides a comprehensive overview of recent advances in thiourea‐amine catalysis in the last five years, highlighting its mechanistic foundations, structural innovations, and expanding functional scope. We first examine computational and experimental insights that have refined the mechanistic understanding of nucleophile and electrophile activation, with emphasis on noncovalent interactions, transition state engineering, and microenvironment effects. Next, we explore the evolution of catalyst architectures, including developments from natural chiral pool scaffolds, modular frameworks for dual activation, and multifunctional designs enabling remote or cooperative reactivity. We also detail recent integrations of thiourea catalysis with photoredox systems, chemoenzymatic cascades, and hybrid metal‐organic platforms, which have enabled new reactivity profiles and stereocontrol mechanisms. Most notably, we discuss the growing application of thiourea catalysts in polymer chemistry and CO 2 conversion, including sequence‐controlled copolymerizations, degradable polyesters, and stimuli‐responsive systems for sustainable materials development. Through critical evaluation of these interdisciplinary advancements, this review outlines current challenges and future directions for thiourea‐amine catalysis, emphasizing its continued evolution as a versatile and sustainable tool in contemporary synthetic chemistry.