Iron‐catalyzed Kumada cross‐coupling reactions of pyrimidin‐2‐yl phosphates and Grignard reagents are described. The reaction proceeds at room temperature with a short reaction time of 15 minutes, and the corresponding products are obtained with moderate to high yields. A wide array of C2‐functionalized pyrimidines has been prepared in moderate to good yields and many functional groups are well tolerated.

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A metal-free synthesis of C2-functionalized pyrimidines via the reaction of pyrimidin-2-yl phosphates with amines and thiophenols in PEG-400 has been developed. The desired products can be generated in good to excellent yields in the environmentally friendly PEG-400, without any catalysts or other additives.

Solvent. -A simple, rapid and environmentally benign procedure for the synthesis of C-2 substituted pyrimidines under catalyst-, base-, and ligand-free conditions is developed. -(XING, T.; WEI, K.-J.; QUAN, Z.-J.; WANG*, X.-C.; Synthesis 47 (2015) 24, 3925-3935, http://dx.

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Pyrimidineand pyridine phosphates react with alkyl and aryl Grignard reagents in the presence of Fe(acac) 3 under mild conditions to give the title compounds at room temperature within 15 minutes. -(XING, T.; ZHANG, Z.; DA, Y.-X.; QUAN*, Z.-J.; WANG, X.-C.; Asian J. Org. Chem. 4 (2015) 6, 538-544, http://dx.