Background: There are a number of protocols for Ullmann coupling–type S-arylation reactions, many of them suffer from the use of homogenous and often corrosive catalyst, cumbersome workup procedures, and long reaction times. Besides, many of these reagents are expensive and non-recoverable, leading to the generation of a large amount of toxic waste particularly when large-scale applications are considered.

Objective: The aim of this study was to prepare a new Pd catalyst bonded on the surface of zeolite as a heterogeneous catalyst.

Methods: A heterogeneous palladium catalyst has been prepared by immobilizing Pd ions on Clinoptilolite. This novel developed heterogeneous catalyst was thoroughly examined for Ullmann coupling–type S-arylation reaction using different bases, solvents and 0.003 mg of the catalyst. The structural and morphological characterizations of the catalyst were carried out using XRD, TGA, BET and TEM techniques.

Results: Highly efficient heterogeneous palladium catalyst has been developed by immobilizing Pd ions on Clinoptilolite, as one of the most abundant naturally occurring zeolites for Ullmann Sarylation. By using this method, we provide an efficient way to a wide variety of substituted thiolic compounds. Moreover, the catalyst is easily recovered using simple filtration and reused for 5 consecutive runs.

Conclusion: In this effort, we developed a new Pd catalyst bonded on the surface of zeolite as a substrate to prepare the heterogeneous catalyst. We demonstrate that this novel catalyst offers reliable and convincing data that may offer a valuable application in further developing the science and technology of Ullmann reaction protocols and allied industries. Additionally, the catalyst was reusable and kept its high activities over a number of cycles.

背景：Ullmann偶联S型芳基化反应有许多方案，其中许多方案使用均相且经常具有腐蚀性的催化剂，繁琐的后处理程序以及较长的反应时间。此外，这些试剂中的许多昂贵且不可回收，导致产生大量有毒废物，尤其是在考虑大规模应用时。

目的：本研究的目的是制备一种新型的结合在沸石表面的钯催化剂，作为非均相催化剂。

方法：通过将钯离子固定在斜发沸石上制备了一种非均相钯催化剂。使用不同的碱，溶剂和0.003 mg的催化剂，对这种新颖开发的多相催化剂进行了Ullmann偶联S型芳基化反应的彻底研究。催化剂的结构和形态表征使用XRD，TGA，BET和TEM技术进行。

结果：通过将Pd离子固定在斜发沸石上开发出了一种高效的多相钯催化剂，这是Ullmann盐基化反应中最丰富的天然沸石之一。通过使用此方法，我们提供了一种有效的方法来制备各种取代的硫醇化合物。此外，使用简单的过滤即可轻松回收催化剂，并可以连续5次重复使用。

结论：在这项工作中，我们开发了一种新型的结合在沸石表面上的Pd催化剂作为基质，以制备非均相催化剂。我们证明了这种新型催化剂提供了可靠且令人信服的数据，这可能在进一步发展Ullmann反应规程和相关产业的科学技术方面提供有价值的应用。另外，该催化剂是可重复使用的，并在多个循环中保持其高活性。