De-Saturation of Single-Atom Copper Catalysts for Accelerating Propargylic Substitution Reactions

Bibliographische Detailangaben
Veröffentlicht in:	Advanced materials (Deerfield Beach, Fla.). - 1998. - (2025) vom: 25. Aug., Seite e09221
1. Verfasser:	Cai, Qilong (VerfasserIn)
Weitere Verfasser:	Meng, Yang, Wu, Chao, Qu, Wenjia, Wang, Qiang, Li, Tan, Liu, Chengyi, Chen, Jinxing, Lin, Huihui, He, Qian, Zhao, Yafei, Xi, Shibo, Lu, Jiong
Format:	Online-Aufsatz
Sprache:	English
Veröffentlicht:	2025
Zugriff auf das übergeordnete Werk:	Advanced materials (Deerfield Beach, Fla.)
Schlagworte:	Journal Article KOH‐mediated Joule thermal de‐saturation strategy propargylic substitution reactions single‐atom catalysts

Beschreibung
Zusammenfassung:	© 2025 The Author(s). Advanced Materials published by Wiley‐VCH GmbH. Rational design of proximal coordination microenvironments surrounding catalytic sites to achieve optimal reaction kinetics represents a paramount pursuit in single-atom catalysts (SACs), yet continues to pose substantial synthetic challenges. Developing innovative strategies that simultaneously stabilize low-coordinated single-metal species on solid supports, while ensuring atomic precision and high activity, remains imperative. Herein, a de-saturation strategy for SACs is demonstrated (denoted as De-sat SACs) using a top-down approach based on a KOH-mediated Joule thermal shock to obtain under-coordinated and asymmetric SACs for efficient organic synthesis. Using copper-based SACs as a proof-of-concept, the de-saturation strategy effectively converts the CuN4 to CuN3 configuration. The De-sat Cu SACs exhibit remarkable catalytic activity in propargylic substitution reactions, tolerating a broad range of nucleophiles (N-, C-, and O-), as well as diverse aryl, alkyl, tertiary, and cyclic propargylic carbonates. The coordination reduction in these De-sat SACs not only breaks the structural symmetry to enhance site accessibility but also elevates the energy of the d z 2 ${d}_{{z}^{2}}$ orbital of Cu atom, thereby facilitating the formation of copper-alkynyl intermediates and boosting their catalytic performance. These findings establish a new platform for the rational design and synthesis of de-saturated yet stable SACs, facilitating challenging catalytic transformations toward sustainable chemical manufacturing
Beschreibung:	Date Revised 25.08.2025 published: Print-Electronic Citation Status Publisher
ISSN:	1521-4095
DOI:	10.1002/adma.202509221