Ru-Mediated and Sulfur-Directed ortho-C–H Activation of Benzyl Thioethers with Internal Alkynes and Selective Hydrothiolation of Acetylene Dicarboxylates

Synthesis Pub Date : 2024-07-22 DOI:10.1055/a-2348-7588
Sangeeta Kumari, Vijesh Tomar, Aditi Soni, Manisha Manisha, Charu Sharma, Raj K. Joshi
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Abstract

In this report, we have established a Ru(η6-C6H6)Cl2 catalysed ortho-C–H activation of benzyl thioethers with alkynes under milder reaction conditions. The sulfur atom of benzyl thioethers worked as a directing group for ortho-C–H activation of benzyl thioethers. The reaction was found to tolerate a range of benzyl thioethers as well as alkynes. Moreover, the reaction is significantly influenced by the length of alkyl and aryl thioethers, with the best results being obtained with benzyl thioethers. Kinetic isotopic experiments suggest that the ortho-C–H bond-breaking is not a rate-determining step for the present reaction. In an unusual observation that has not been reported, apart from ortho-C–H activation, under the same reaction conditions, a selective debenzylative hydrothiolation was exclusively obtained with acrylates, which broadens the synthetic impact of benzyl thioethers for the preparation of mixed chalcogen ethers.

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Ru 介导和硫引导的苄基硫醚与内部炔烃的正交-C-H 活化反应以及乙炔二羧酸盐的选择性氢硫化反应
在本报告中,我们在较温和的反应条件下建立了 Ru(η6-C6H6)Cl2 催化苄基硫醚与炔烃的正交-C-H 活化反应。硫代苄基醚的硫原子可作为硫代苄基醚正交-C-H 活化的定向基团。研究发现,该反应对一系列硫代苄基物和炔烃都有耐受性。此外,该反应受烷基和芳基硫醚长度的影响很大,苄基硫醚的效果最好。动力学同位素实验表明,正交-C-H 键的断裂并不是本反应的速率决定步骤。在相同的反应条件下,除了正交-C-H 键活化外,丙烯酸酯还能选择性地发生去苄基硫代氢硫化反应,这在制备混合缩醛醚方面扩大了苄基硫醚的合成影响。
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