Scalable α-Arylation of Nitriles in Aqueous Micelles using Ultrasmall Pd Nanoparticles: Surprising Formation of Carbanions in Water
Scalable α-Arylation of Nitriles in Aqueous Micelles using Ultrasmall Pd Nanoparticles: Surprising Formation of Carbanions in Water
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DOI：
10.1021/acscatal.0c01196
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发表时间：
2020-06-19
期刊：
影响因子：
12.9
通讯作者：
Handa, Sachin
中科院分区：
文献类型：
--
作者：
Bihani, Manisha;Ansari, Tharique N.;Handa, Sachin
描述了一种可扩展的合成方法，既可以制备超小的钯纳米颗粒，又可以将其用于催化水胶束中腈的α-芳基化反应。这种方法涉及到碳负离子或酮亚胺的中间体，它们可能是由胶束环境稳定的，而不是用水淬灭的。对这些Pd纳米粒子进行了彻底的表征。P-31核磁共振波谱的机理研究揭示了膦配体与钯表面的结合，对照实验证实了钯的零氧化态。通过35个例子展示了转换的范围，其中包括一个50g规模的例子。
A scalable synthetic method is described for both the preparation of ultrasmall palladium nanoparticles and their subsequent use in catalyzing an alpha-arylation reaction of nitriles in aqueous micelles. This method involves the intermediacy of carbanions or keteniminates, which are presumably stabilized by the micellar environment rather than being quenched with water. These Pd nanoparticles are thoroughly characterized. Mechanistic studies using P-31 NMR spectroscopy revealed the binding of phosphine ligand with the Pd surface and control experiment confirmed the zero-oxidation state of palladium. The scope of the transformation is demonstrated over 35 examples, including one at 50 g scale.