Selective reductions of cyclic 1,3-diesters using SmI(2) and H(2)O.
SmI(2)-H(2)O reduces cyclic 1,3-diesters to 3-hydroxyacids with no over-reduction. Furthermore, the reagent system is selective for cyclic 1,3-diesters over acyclic 1,3-diesters and esters. Experimental and computational studies suggest that the origin of the selectivity lies in the initial electron transfer to the ester carbonyl and the anomeric stabilization of the resulting radical-anion intermediate. Radicals formed by one-electron reduction of the ester carbonyl group have been exploited in intramolecular additions to alkenes.
Guazzelli
Giuditta
G
School of Chemistry, University of Manchester, UK.
De Grazia
Sara
S
Collins
Karl D
KD
Matsubara
Hiroshi
H
Spain
Malcolm
M
Procter
David J
DJ
D004952:Esters / Q000737:chemistry*; D005609:Free Radicals; D006880:Hydroxy Acids / Q000138:chemical synthesis; D007454:Iodides / Q000737:chemistry; D019163:Reducing Agents / Q000737:chemistry*; D012493:Samarium / Q000737:chemistry; D014867:Water / Q000737:chemistry
D004952:Esters; D005609:Free Radicals; D006880:Hydroxy Acids; D007454:Iodides; D019163:Reducing Agents; D014867:Water; D012493:Samarium; C409809:samarium diiodide