Follow the Silyl Cation: Insights into the Vorbrüggen Reaction

To succeed in the development of a mechanistic model for the Vorbrüggen reaction of thymine with an advanced furanose intermediate, a range of spectroscopic techniques were applied and found essential to understanding kinetically relevant, yet nonisolable, silylated reaction intermediates. Understanding of the dynamic nature of the interaction of trimethylsilyl trifluoromethanesulfonate with these functionally dense substrates allowed for the accurate prediction and straightforward explanation of the relationship between process parameters and the levels of key impurities.