Lithiations and Grignard Reactions on Pyrimidine and Quinazoline

Pyrimidine and quinazoline structural motifs are abundantly found in naturally occurring compounds, with uracil, thymine, and cytosine being the most prominent representatives. Furthermore, the pyrimidine core constitutes a subunit of many compounds rendering substantial medicinal or economic benefits. This review focuses on lithiations and Grignard reactions as tools for selective yet variable purposive derivatizations of pyrimidine and quinazoline, excluding stochiometric transmetalations. A brief introduction into the topic is followed by a detailed summary of what has been done in the field since 2005. The chemistry is discussed in several sections based on the structure of the substrates, which is expected to simplify orientation in the text. Deprotonative and halogen–metal exchange metalations, respectively, are reported separately for each major group of the substrates.