Oxidations with Oxone: solvent-mediated switching between oxidative addition (β-hydroxysulfides) and addition–oxidation (β-arylsulfones) of thiols to olefins Navin Yadav 1 , Soumen Payra 1 , Jarugu Narasimha Moorthy 1,2 1 Indian Institute of Technology, India, 2 Indian Institute of Science Education and Research, India Control of selectivity and regulation of product outcome in a desirable manner with reactive intermediates is challenging.Solvents exert a remarkable influence on the occurrence as well as the mechanism of reactions. 1 In continuation of our research on oxidations with IBX and Oxone, 2 we have found that in biphasic medium toluene:water (9:1, v/v), the reaction of aryl olefins with thiols in the presence of Oxone proceeds through a thiyl radical intermediate generated by oxidation of thiols with Oxone, which is intercepted by aryl olefins to afford β-hydroxy-2-arylethyl aryl sulphides smoothly.However, the change in reaction solvent to acetonitrile:water (9:1, v/v) is shown to facilitate a concerted and non-radical pathway leading to 2-arylethyl aryl sulfonesexclusively via a tandem thiol-ene ‘click’ reaction followed by oxidation. The novelty of these reactions is the promotion of ‘oxidative addition’ in toluene:water medium and ‘addition–oxidation’ in acetonitrile:water. As Oxone is cheap, readily available, and environmentally benign, solvent-mediated switchable selectivity constitutes facile and direct access to two synthetically important products, namely, 2-arylethyl aryl sulfones 3 and β-hydroxy-2-arylethyl aryl sulfides. 4 References 1. Wang, Q. Lu, C. Qian, C. Liu, W. Liu, K. Chen, and A. Lei, Angew. Chem., Int. Ed ., 2016 , 55 , 1094–1097. 2. (a) K. N. Parida and J. N. Moorthy, Tetrahedron , 2014 , 68 , 2280–2285; (b) K. N. Parida and J. N. Moorthy, Org. Chem ., 2015 , 80 , 8354–8360; (c) J. N. Moorthy, K. Senapati and S. Kumar, J. Org. Chem., 2009 , 74 , 6287–6290; (d) J. N. Moorthy, K. Senapati, K. N. Parida, S. Jhulki, K. Sooraj and N. N. Nar, J. Org. Chem ., 2011 , 76 , 9593–9601. 3. Zheng, Y. You, Q. Shen, J. Zhang, L. Liu and X.-H. Duan, Org. Chem. Front. , 2020 , 7 , 2069–2074. 4. S. Payra, N. Yadav and J. N. Moorthy, New J. Chem., 2022 , 46 , 582–591.
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