The Stability and Reactivity of Activated Acryloylcarbamates as Reagents for the Synthesis of N-1 Substituted Thymine and Uracil - An NMR and DFT Study

Dominik Rejman (1) , Radek Pohl (2) , Lubomír Rulíšek (3)

1 Medicinal Chemistry II
2 Dept. of NMR
3 Computational Chemistry

The mechanism of the decomposition of novel reagents for convenient synthesis of 1-N-substitued thymine and uracil derivatives yielding highly reactive isocyanates was proposed based on NMR measurements and quantum chemical calculations. A good agreement between the experimental kinetic data and DFT calculations allowed us to demonstrate that the stability of the reagents depends on the presence of methyl in acryloyl moiety and position of nitro group in nitrophenolic part of molecule. Furthermore, the reactivity of the reagents with low nucleophilic and sterically hindered 2,4,6-tri-tert-butylaniline was explored by 1H NMR demonstrating the usefulness of the reagents offering access to a variety of 1 N substituted uracils and thymines with potentially interesting biological properties.

Mots clés: Physical Sciences

Dominik Rejman, Radek Pohl, Lubomír Rulíšek. The Stability and Reactivity of Activated Acryloylcarbamates as Reagents for the Synthesis of N-1 Substituted Thymine and Uracil - An NMR and DFT Study. Journal of Physical Organic Chemistry, 2010, 24 (5), pp.423. ⟨10.1002/poc.1775⟩. ⟨hal-00599797⟩