Investigation of novel methods for stereoselective synthesis involving radical translocation

WCC 18

Rebecca R. Parkhurst, Hamilton College, Clinton, NY 13323 and Ian Rosenstein, IRosenst@hamilton.edu, Department of Chemistry, Hamilton College, 198 College Hill Rd, Clinton, NY 13323.
The reaction of N-acylated chiral 4-hydroxymethyl-2-oxazolidinones under radical conditions using diiodoacetoxybenzene (DIB) and light was investigated. We hypothesize that 1,6-radical translocation will occur by abstraction of a hydrogen alpha to the carbonyl by the alkoxy radical generated from the alcohol of the hydroxymethyl group. The steric bulk of the oxazolidinone moiety will then allow for stereoselective addition at the new radical position. The simplest member of this family of molecules, that which contains an unsubstituted hydroxymethyl group, was synthesized via a 6-step process. This compound will be the least likely to undergo β-fragmentation instead of hydrogen abstraction, but will also provide the least stereocontrol. To test the hypothesis we have submitted N-acylated prolinol to the same radical conditions using allyl tributyltin as a radical trap and have seen interesting allylation by 1H NMR.
 

Many Faces of Chemistry: Merck Index Women in Chemistry
1:00 PM-3:00 PM, Monday, August 20, 2007 BCEC -- Exhibit Hall - B2, Poster

Women Chemists Committee

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007