Peracid oxidation of unactivated sp3 C—H bonds: an important solvent effect

Sergej Maciuk, Susanna H. Wood, Vipulkumar K. Patel, Peter D. P. Shapland, Nicholas C. O. Tomkinson

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)
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Abstract

The peracid oxidation of hydrocarbons in chlorinated solvents is a low yielding and poorly selective process. Through a combination of DFT calculations, spectroscopic studies, and kinetic measurement it is shown that the origin of this is electronic in nature and can be influenced through the addition of hydrogen bond donors (HBD) and hydrogen bond acceptors (HBA). Performing the reaction of a cycloalkane with mCPBA in a fluorinated alcohol solvent such as nonafluoro-tert-butanol (NFTB) or hexafluoroisopropanol (HFIP), which act as strong HBD and poor HBA, leads to significantly higher yields and selectivities being observed for the alcohol product. Application of the optimised reaction conditions allows for the selective oxidation of both cyclic and linear alkane substrates delivering the corresponding alcohol in up to 86 % yield. The transformation shows selectivity for tertiary centres over secondary centres and the oxidation of secondary centres is strongly influenced by stereoelectronic effects. Primary centres are not oxidised by this method. A simple computational model developed to understand this transformation provides a powerful tool to reliably predict the influence of substitution and functionality on reaction outcome.
Original languageEnglish
Article numbere202204007
Number of pages9
JournalChemistry - A European Journal
Volume29
Issue number31
Early online date8 Mar 2023
DOIs
Publication statusPublished - 2 Jun 2023

Keywords

  • oxidation
  • perfluorinated solvents
  • peroxides
  • reaction mechanisms
  • solvent effects

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