A variety of pyrimidine derivatives can be easily prepared starting from commercially available 2-bromopyrimidine [7] (2). The treatment of 2 with TMPMgCl˙LiCl (1, 1.1 equiv, -60 ˚C, 1.5 h) leads to the 4-magnesiated pyrimidine 4, which can be trapped by electrophiles such as S-phenyl benzenethiosulfonate, iodine, or 1,1,2-trichloro-1,2,2-trifluoroethane furnishing the functionalized pyrimidines 5a-c in 71-80%. The formation of a new CC bond can be easily performed by ...
