Oxadiazinones as chiral auxiliaries: Efforts toward the synthesis of a key intermediate in the biosynthetic pathway to coumarin

ORGN 459

Shawn Hitchcock and Trisha R. Hoover. Department of Chemistry, Illinois State University, Campus Box 4160, Normal, IL 61790-4160

The synthesis and application of chiral auxiliaries is an important facet in synthetic organic chemistry. Our group is interested in developing compounds known as 3,4,5,6-tetrahydro-2H,1,3,4-oxadiazin-2-ones as chiral auxiliaries for use in asymmetric organic synthesis. We have demonstrated that the N3-propionyl system can serve as a chiral auxiliary in the asymmetric aldol addition. The yields were good and the observed diastereoselectivities ranged from 3:1 to 99:1. These results lead to the investigation of conducting the aldol addition reaction with other N3-acyl substituents. We have synthesized and acylated a 3,4,5,6-tetrahydro-2H,1,3,4-oxadiazin-2-one derived from enantiomerically pure ephedrine. It has been shown that it is possible to employ various N3-glycolyl derivatives in the asymmetric aldol addition reaction with good yield and reasonable diastereoselectivities. The N3-α-haloacetyl system was also examined in the asymmetric aldol addition. This synthetic methodology was then employed in the synthesis of a key intermediate in the biosynthetic pathway to Coumarin.

Total Synthesis, Asymmetric Reactions and Syntheses, Bioorganic 9:00 AM-11:00 AM, Wednesday, March 31, 2004 Anaheim Convention Center -- Hall C, Poster Division of Organic Chemistry The 227th ACS National Meeting, Anaheim, CA, March 28-April 1, 2004