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金催化炔烃水合反应中使用腔状膦配体的形状选择性。

Shape Selectivity in the Gold-Catalyzed Hydration of Alkynes Using a Cavity-Shaped Phosphine.

机构信息

Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Sevilla and Consejo Superior de Investigaciones Científicas (CSIC)., Avenida Américo Vespucio 49, 41092, Sevilla, Spain.

Institute of Applied Chemistry, Department of Science and Technology, IMC University of Applied Sciences., Krems, 3500, Austria.

出版信息

Chempluschem. 2023 Jul;88(7):e202300231. doi: 10.1002/cplu.202300231.

Abstract

A cavity-shaped gold(I) complex derived from a bulky tri-(ortho-biaryl)-phosphine ligand shows preferred selectivity towards terminal functionalities in the gold(I)-catalysed hydration of alkynes under mild heating due to a well-defined pocket as catalytic active site. The confinement-induced size-exclusion selectivity investigated for eight alkynes contrasts with other gold(I) complexes bearing bulky phosphine ligands that show reduced selectivity or even similar behaviour towards both internal and terminal alkynes. We also interrogate the potential of gold(III) derivatives for the same catalytic process.

摘要

一个具有空腔结构的金(I)配合物,由一个庞大的三(邻位-联芳基)-膦配体衍生而来,由于其作为催化活性位点的明确口袋,在温和加热条件下,在金(I)催化炔烃水合反应中,对末端官能团表现出优先选择性。在对八种炔烃进行的受限诱导的尺寸排除选择性研究中,与其他带有庞大膦配体的金(I)配合物形成对比,后者对内部和末端炔烃的选择性降低,甚至表现出相似的行为。我们还研究了金(III)衍生物在相同催化过程中的潜力。

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