Elemental fluorine and HOF·CH3CN in service of general organic chemistry

Shlomo Rozen*

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

Abstract

At present, HOF·CH3CN complex is the best oxygen transfer agent that chemistry has to offer. It is readily made by passing dilute fluorine through aqueous acetonitrile and does not require any isolation or purification. It is stable in aqueous acetonitrile solution for a few hours at room temperature, providing ample opportunities for various reactions. Epoxidation of regular olefins as well as of very electron-depleted ones proceeds smoothly. HOF·CH3CN transfer oxygen also to heteroatoms, especially sulfur and nitrogen. Even very electron-depleted sulfides such as RfSAr that are very difficult to oxidize, are converted into the respective sulfones in a matter of minutes. On the other hand, since the reaction conditions are very mild, the reagent can oxidize various thiophenes and amino acids to the corresponding S,S-dioxides and α-nitro acid derivatives. HOF·CH3CN was also instrumental in ending the 50 years quest for making the elusive 1,10-phenanthroline N,N-dioxide and for the novel transformation of azides to nitro derivatives. The use of BrF3 for making symmetric esters and of tBuOF as an electrophilic tert-butoxylation agent is also mentioned.

Original languageEnglish
Pages (from-to)2433-2447
Number of pages15
JournalEuropean Journal of Organic Chemistry
Issue number12
DOIs
StatePublished - 13 Jun 2005

Keywords

  • Fluorine
  • Hypofluorous acid
  • Oxygenation

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