A diverse collection of tetracycline derivatives has been synthesized utilizing Heck, Suzuki, and other palladium-coupling reactions via tetracycline arenediazonium and iodoarene salts. Large numbers of tetracyclines are now possible via these reactions, including numerous upper periphery derivatives of doxycycline, minocycline, sancycline, and methacycline modified at positions C7, C9, and C6-C13 on the tetracycline naphthacene ring. Application of palladium-coupling reactions to the tetracyclines has yielded new tetracycline classes with differing structural attributes, greatly increasing the structural diversity of this family of antibiotics, one of the last of the early antibiotic families to be expanded by organic and medicinal chemistry.

We report the synthesis of 2-chloro-5-pyrimidylboronic acid (6) and 2-amino-5-pyrimidylboronic acid (8) by lithium-halogen exchange followed by reaction with triisopropylborate. Their reactivity with heteroaryl halides in Suzuki-Miyaura cross-coupling reactions has been evaluated. New highly functionalized 5-heteroarylpyrimidine derivatives 24-33

Pyrimidine derivatives R 0510 New Pyrimidylboronic Acids and Functionalized Heteroarylpyrimidines by Suzuki Cross-Coupling Reactions. -Two new pyrimidylboronic acid derivatives (II) are prepared and used in Suzuki-Miyaura cross-coupling with a range of hetaryl halides. -(CLAPHAM, K. M.; SMITH, A. E.; BATSANOV, A. S.; MCINTYRE, L.; POUNTNEY, A.; BRYCE*, M. R.; TARBIT, B.; Eur. J. Org. Chem. 2007, 34, 5712-5716; Dep. Chem., Univ. Durham, Durham DH1 3LE, UK; Eng.) -Bartels 13-156