The stability and reactivity of activated acryloylcarbamates as reagents for the synthesis of N-1 substituted thymine and uracil - an NMR and DFT study

0359404 - ÚOCHB 2012 RIV GB eng J - Journal Article
Pohl, Radek - Rulíšek, Lubomír - Rejman, Dominik
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. Roč. 24, č. 5 (2011), s. 423-430. ISSN 0894-3230. E-ISSN 1099-1395
R&D Projects: GA MŠMT 2B06065; GA MŠMT LC512
Institutional research plan: CEZ:AV0Z40550506
Keywords : mechanism * NMR * nucleosidation
Subject RIV: CC - Organic Chemistry
Impact factor: 1.963, year: 2011

The mechanism of the decomposition of acryloylcarbamates 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 7a-d depends on the presence ofmethyl in the acryloylmoiety and the position of the nitro group in the nitrophenolic part of themolecule. Furthermore, the reactivity of these reagents with weakly nucleophilic and sterically hindered 2,4,6-tri-tert-butylaniline was explored by 1H NMR demonstrating the usefulness of reagents 7a-d offering access to a variety of 1-N-substituted uracils and thymines with potentially interesting biological properties.
Permanent Link: http://hdl.handle.net/11104/0197201