Publications by authors named "Sergio Sisti"

A product and DFT computational study on the reactions of 3-ethyl-3-(trifluoromethyl)dioxirane (ETFDO) with bicyclic and spirocyclic hydrocarbons bearing cyclopropyl groups was carried out. With bicyclo[.1.

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Article Synopsis
  • A comprehensive study details C(sp)-H bond oxygenation reactions utilizing the [Mn(OTf)(mcp)] complex, focusing on methylenic sites in various cycloalkyl and 1-alkyl substrates with 19 different electron-withdrawing functional groups (EW FGs).
  • The research compares the effectiveness of these reactions in acetonitrile (MeCN) versus strong hydrogen bond donating solvents, finding significantly better yields and site-selectivities in the latter.
  • It establishes a novel method for achieving high site-selectivity and yield in oxidation reactions, allowing for extensive application across different substrate classes under mild conditions, enhancing synthesis strategies in organic chemistry.
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A kinetic study of the hydrogen atom transfer (HAT) reactions from nitrogen-containing heterocycles (secondary and tertiary lactams, 2-imidazolidinones, 2-oxazolidinones, and succinimides) to the cumyloxyl radical has been carried out employing laser flash photolysis with ns time resolution. HAT occurs from the C-H bonds that are α to nitrogen, activated by hyperconjugative overlap with the N-C═O π system. In the lactam series, the second-order HAT rate constant () was observed to decrease by a factor of ∼4 going from the five- and six-membered ring derivatives to the eight-membered ones, a behavior that was rationalized on the basis of a reduced extent of hyperconjugative activation associated to the greater flexibility of the larger rings compared to the smaller ones.

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