Selective functionalisation of saturated C-H bonds with metalloporphyrin catalysts

Chem Soc Rev. 2011 Apr;40(4):1950-75. doi: 10.1039/c0cs00142b. Epub 2011 Mar 9.

Abstract

The recent surge of interest in metal-catalysed C-H bond functionalisation reactions reflects the importance of such reactions in biomimetic studies and organic synthesis. This critical review focuses on metalloporphyrin-catalysed saturated C-H bond functionalisation reported since the year 2000, including C-O, C-N and C-C bond formation via hydroxylation, amination and carbenoid insertion, respectively, together with a brief description of previous achievements in this area. Among the metalloporphyrin-catalysed reactions highlighted herein are the hydroxylation of steroids, cycloalkanes and benzylic hydrocarbons; intermolecular amination of steroids, cycloalkanes and benzylic or allylic hydrocarbons; intramolecular amination of sulfamate esters and organic azides; intermolecular carbenoid insertion into benzylic, allylic or alkane C-H bonds; and intramolecular carbenoid C-H insertion of tosylhydrazones. These metalloporphyrin-catalysed saturated C-H bond functionalisation reactions feature high regio-, diastereo- or enantioselectivity and/or high product turnover numbers. Mechanistic studies suggest the involvement of metal-oxo, -imido (or nitrene), and -carbene porphyrin complexes in the reactions. The reactivity of such metal-ligand multiple bonded species towards saturated C-H bonds, including mechanistic studies through both experimental and theoretical means, is also discussed (244 references).

Publication types

  • Research Support, Non-U.S. Gov't
  • Review

MeSH terms

  • Amination
  • Carbon / chemistry*
  • Catalysis
  • Hydrogen / chemistry*
  • Hydroxylation
  • Metalloporphyrins / chemistry*
  • Methane / analogs & derivatives
  • Methane / chemistry

Substances

  • Metalloporphyrins
  • carbene
  • Carbon
  • Hydrogen
  • Methane