Dihydropyranone formation by ipso C-H activation in a glucal 3-carbamate-derived rhodium acyl nitrenoid

J Org Chem. 2011 Apr 1;76(7):2240-4. doi: 10.1021/jo101599q. Epub 2011 Mar 7.

Abstract

By using (N-tosyloxy)-3-O-carbamoyl-D-glucal 10, which removes the need for a hypervalent iodine(III) oxidant, we provide evidence for rhodium nitrenoid-mediated ipso C-H activation as the origin of a C3-oxidized dihydropyranone product 3. This system may be especially susceptible to such a pathway because of the ease of forming a cation upon hydride transfer to the rhodium-complexed acyl nitrene.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Calcium Gluconate / chemistry*
  • Carbamates / chemistry*
  • Carbonates / chemistry
  • Catalysis
  • Hydrogen Bonding
  • Kinetics
  • Molecular Structure
  • Organometallic Compounds / chemistry*
  • Oxidants / chemistry*
  • Potassium / chemistry
  • Rhodium / chemistry*
  • Tosyl Compounds / chemistry*

Substances

  • (N-tosyloxy)-3-O-carbamoyl-D-glucal
  • Carbamates
  • Carbonates
  • Organometallic Compounds
  • Oxidants
  • Tosyl Compounds
  • potassium carbonate
  • Rhodium
  • Potassium
  • Calcium Gluconate