薗头偶联反应
催化作用
化学
钯
组合化学
配体(生物化学)
芳基
多相催化
纳米技术
有机化学
材料科学
生物化学
烷基
受体
作者
Dario Poier,Dario Faust Akl,Elysia Lucas,A. Machado,Georgios Giannakakis,Sharon Mitchell,Gonzalo Guillén‐Gosálbez,Roger Martí,Javier Pérez‐Ramírez
出处
期刊:ACS Sustainable Chemistry & Engineering
[American Chemical Society]
日期:2023-11-22
卷期号:11 (48): 16935-16945
标识
DOI:10.1021/acssuschemeng.3c04183
摘要
Single-atom heterogeneous catalysts (SACs) attract growing interest in their application in green chemistry and organic synthesis due to their potential for achieving atomic-level precision. These catalysts offer the possibility of achieving selectivity comparable to the traditionally applied organometallic complexes, while enhancing metal utilization and recovery. However, an understanding of SAC performance in organic reactions remains limited to model substrates, and their application as drop-in solutions may not yield optimal activity. Here, we investigate the previously unaddressed influence of the reaction environment, including solvent, base, cocatalyst, and ligand, on the performance of a palladium SAC in Sonogashira–Hagihara cross-couplings. By examining the effects of different solvents using the established criteria, we find that the behavior of the SAC deviates from trends observed with homogeneous catalysts, indicating a distinct interplay between heterogeneous systems and the reaction environment. Our results illustrate the satisfactory performance of SACs in cross-couplings of aryl iodides and acetylenes with electron-withdrawing and -donating groups, while the use of bromides and chlorides remains challenging. Extending the proof-of-concept stage to multigram scale, we demonstrate the synthesis of an intermediate of the anticancer drug Erlotinib. The catalyst exhibits high stability, allowing for multiple reuses, even under noninert conditions. Life-cycle assessment guides the upscaling of the catalyst preparation and quantifies the potential environmental and financial benefits of using the SAC, while also revealing the negligible impact of the PPh3 ligand and CuI cocatalyst. Our results underscore the significant potential of SACs to revolutionize sustainable organic chemistry and highlight the need for further understanding the distinct interplay between their performance and the reaction environment.
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