Chemoselective Reduction of Organic Sulphoxides, Selenoxides and Telluoxides with Magnesium in Methanolic Media and its Mechanistic Insights Organic Chemistry
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Abstract
Mercuric chloride catalysed, a versatile, convenient and practical procedure has been developed for the reduction of chalcogenide monoxides, including sulphoxides, selenoxides and telluroxides into their respective chalcogenides. The reaction is performed using magnesium metal as the reducing agent in methanol at ambient temperature. The procedure demonstrates wide functional group tolerance and proceed under straight forward reaction conditions, making it well fitted for synthetic applications. Notably, sulphoxides required a relatively higher amount of magnesium compared to their selenium and tellurium congeners, indicating a clear difference in reactivity among the chalcogen series. The reactions proceed rapidly and proposed to be proceeding via Single Electron Transfer (SET) mechanism initiated by magnesium. This mechanism is further supported by theoretical calculations, predicted by Gaussian 09 with B3LYP/6-31G (d,p) level of theory, which indicates the role of HOMO-LUMO interactions in triggering the electron transfer. The methodology shows high chemselectivity, wide functional group tolerance under the reaction conditions and no instances of deselenization, detellurization, or desulphurization product were found, signifying the stability of chalcogenide products.
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