Dramatic effect of solvent hydrogen bond basicity on the regiochemistry of S(N)Ar reactions of electron-deficient polyfluoroarenes

Org Lett. 2009 Dec 17;11(24):5662-4. doi: 10.1021/ol902353t.

Abstract

It was found that solvent hydrogen bond basicity (SHBB) significantly affects the regiochemistry of the S(N)Ar reaction between secondary amines and activated polyfluoroarenes. A plausible mechanism involving a six-membered transition state is invoked for the formation of an ortho-substituted isomer, which is likely organized by a hydrogen bond. Evidence for this hypothesis is presented, and a regioselective amination reaction of activated polyfluoroarenes has been developed.

MeSH terms

  • Hydrocarbons, Fluorinated / chemical synthesis
  • Hydrocarbons, Fluorinated / chemistry*
  • Hydrogen Bonding
  • Molecular Structure
  • Solvents / chemistry
  • Stereoisomerism

Substances

  • Hydrocarbons, Fluorinated
  • Solvents