36th Annual Student Research Conference
Computational Investigation of the Tautomerization of Carbamoyl Derivatives of Troger’s Base
Kara Sargent* and Sami W. Charleville
Dr. Stuart Winikoff, Faculty Mentor
Tröger’s base (TB) is a C2 symmetric, bicyclic, V-shaped molecule that exhibits chirality from pyramidal nitrogen atoms which are structurally incapable of undergoing inversion. University of Missouri’s Harmata group developed a synthesis for the thermodynamically favored exo addition of carbamoyl groups onto TB that can tautomerize into the kinetically favored endo-isomer. This isomer shows potential as an effective ligand for metal-based catalysts. The tautomerization reaction consists of exposure to basic conditions followed by a protic quench to produce the endo-isomer. However, this methodology only produces up to 86% yield with low stereospecificity. To increase yields and stereospecificity, conditions of the protic quench and basic conditions were investigated computationally. Furthermore, effects of steric hindrance were elucidated from differences in the R-group size on the carbamoyl moiety. Computational results indicate that stereochemical products appear to be controlled by the deprotonation step and carbamoyl stabilization.
Keywords: Tröger’s base, Computational chemistry, Organic chemistry, Tautomerization, Stereochemistry
Topic(s):Chemistry
Presentation Type: Oral Presentation
Session: 107-2
Location: MG 2001
Time: 8:45