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Hybrid hydrogels loaded with palladium nanoparticles – Catalysts for environmentally-friendly Sonogashira and Heck cross-coupling reactions
Tetrahedron ( IF 2.1 ) Pub Date : 2020-06-26 , DOI: 10.1016/j.tet.2020.131344
Petr Slavik , David K. Smith

Palladium nanoparticles (PdNPs) were encapsulated within hybrid hydrogels made from an acylhydrazide-functionalised 1,3:2,4-dibenzylidene sorbitol (DBS-CONHNH2) low-molecular-weight gelator (LMWG) combined with agarose polymer gelator via in situ reduction of Pd(II). These heterogeneous gel-phase catalysts were successfully applied for copper-, amine- and phosphine-free Sonogashira cross-coupling reactions under environmentally-friendly conditions without the need for inert atmosphere reaction conditions. The PdNP-loaded gel was reused in Sonogashira couplings up to at least five times with no adverse effect on yield. The performance of solvated PdNP-loaded gel catalysts was compared with the dried xerogels. The xerogels can be used at higher temperatures, enhancing reaction kinetics albeit lowering reaction selectivity, but unlike the solvated gels, were unable to be easily recycled and reused. The PdNP-loaded gels also had good activity in Heck reactions, and although longer reaction times or higher temperatures were required than for the Sonogashira reaction, the reaction conditions were mild for a Heck coupling. In summary, we demonstrate a ‘waste-to-wealth’ methodology in which Pd(II) ‘waste’ is converted into a valuable gel-phase catalyst that can be used for green Sonogashira and Heck cross-coupling reactions.



中文翻译:

载有钯纳米粒子的杂化水凝胶–环保型Sonogashira和Heck交叉偶联反应的催化剂

2,4-二亚苄基山梨糖醇(DBS-CONHNH:钯纳米颗粒(PdNPs)购自酰肼-官能化的1,3-制成混合水凝胶内封装2)低分子量胶凝剂(LMWG)琼脂糖凝胶因子聚合物经由合并的原位还原Pd(II)。这些多相凝胶相催化剂已成功用于环保条件下的无铜,无胺和膦的Sonogashira交叉偶联反应,而无需惰性气氛反应条件。负载PdNP的凝胶可在Sonogashira偶联剂中重复使用至少5次,而对收率无不利影响。将溶剂化的负载PdNP的凝胶催化剂的性能与干燥的干凝胶进行了比较。所述干凝胶可以在更高的温度下使用,尽管降低了反应的选择性,但可以提高反应动力学,但与溶剂化的凝胶不同,它们不易于回收和再利用。装有PdNP的凝胶在Heck反应中也具有良好的活性,尽管比Sonogashira反应需要更长的反应时间或更高的温度,对于Heck偶联,反应条件温和。总而言之,我们展示了一种“从废物到财富”的方法,其中Pd(II)“废物”被转化成有价值的凝胶相催化剂,可用于绿色Sonogashira和Heck交叉偶联反应。

更新日期:2020-06-26
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