Determination of the Reaction Mechanism for the Tautomerization of Tröger's Base
Location
Oyate Hall
Event Website
https://2026undergraduateresearchsy.sched.com/event/2Ix95/determination-of-the-reaction-mechanism-for-the-tautomerization-of-trogers-base
Start Date
15-4-2026 6:00 PM
End Date
15-4-2026 8:00 PM
Description
Tröger’s base is a V-shaped, bicyclic, chiral molecule that has the unique flexibility to have derivatives added to its carbon backbone. This allows for Tröger’s base to be used in many material applications, such as chemical dopants, molecular sensors, and selective membranes. This research focuses on the addition of a carbamoyl group (-CONEt2) to Tröger’s base that generates two conformations, either an endo- or exo-isomeric form, based upon the relationship of the carbamoyl group to the carbon backbone. The endo-derivative based on its structure, with the carbamoyl pointing into the V of the molecule, allows for the additional nitrogen to better coordinate and react with metals, which could be used to build a new generation of catalysts. The exo-derivative of Tröger’s base is shown to be the more stable species. However, recent work has shown that the endo-derivative can be selectively produced by sequential proton transfer under cold, highly basic conditions. This tautomerization happens through two mechanistic steps: deprotonation using diisopropylamine followed by a protic quench using methanol. Prior research has predicted that this reaction proceeds through a charged enolate intermediate, but has not shown a clear mechanism for selectivity of the endo-product. This project investigated the impact that lithium cations have on the reaction pathway. We found that including lithium coordination to the reaction complexes, as well as adjusting the energy outputs to account for a colder reaction temperature, produced a reaction pathway that better agreed with experimental results. This could potentially allow use of lithium salts to increase the yield of endo-species in the future allowing research into novel applications as a catalyst.
Publication Date
2026
Determination of the Reaction Mechanism for the Tautomerization of Tröger's Base
Oyate Hall
Tröger’s base is a V-shaped, bicyclic, chiral molecule that has the unique flexibility to have derivatives added to its carbon backbone. This allows for Tröger’s base to be used in many material applications, such as chemical dopants, molecular sensors, and selective membranes. This research focuses on the addition of a carbamoyl group (-CONEt2) to Tröger’s base that generates two conformations, either an endo- or exo-isomeric form, based upon the relationship of the carbamoyl group to the carbon backbone. The endo-derivative based on its structure, with the carbamoyl pointing into the V of the molecule, allows for the additional nitrogen to better coordinate and react with metals, which could be used to build a new generation of catalysts. The exo-derivative of Tröger’s base is shown to be the more stable species. However, recent work has shown that the endo-derivative can be selectively produced by sequential proton transfer under cold, highly basic conditions. This tautomerization happens through two mechanistic steps: deprotonation using diisopropylamine followed by a protic quench using methanol. Prior research has predicted that this reaction proceeds through a charged enolate intermediate, but has not shown a clear mechanism for selectivity of the endo-product. This project investigated the impact that lithium cations have on the reaction pathway. We found that including lithium coordination to the reaction complexes, as well as adjusting the energy outputs to account for a colder reaction temperature, produced a reaction pathway that better agreed with experimental results. This could potentially allow use of lithium salts to increase the yield of endo-species in the future allowing research into novel applications as a catalyst.
https://digitalcommons.morris.umn.edu/urs_event/2026/posters/9