A versatile methodology for the regioselective C⁸-metalation of purine bases.
Purine nucleobases are excellent ligands for metal ions, forming normally coordinative Werner-type bonds by utilizing the N donor atoms of the nucleobase skeleton. Here we show that purines such as 8-chlorocaffeine and 8-bromo-9-methyladenine react with [Pt(PPh3)4] under oxidative addition of the C(8)-halogen bond to the metal center. The resulting Pt(II) complexes feature a C(8)-bound ylidene ligand. Protonation of the ylidene at the N(7/9)-atom yields complexes bearing a protic N-heterocyclic carbene ligand derived from the purine base with an NMe,NH-substitution pattern.
Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster , D-48149 Münster, Germany.
Dirk
D
Brackemeyer
Alexandre
A
Hervé
Christian
C
Schulte to Brinke
Mareike C
MC
Jahnke
F Ekkehardt
FE
Hahn
D006571:Heterocyclic Compounds / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D017671:Platinum Compounds / Q000138:chemical synthesis / Q000737:chemistry; D011684:Purine Nucleosides / Q000737:chemistry; D011685:Purine Nucleotides / Q000737:chemistry; D011687:Purines / Q000138:chemical synthesis* / Q000737:chemistry; D014961:X-Ray Diffraction
D006571:Heterocyclic Compounds; D008670:Metals; D017671:Platinum Compounds; D011684:Purine Nucleosides; D011685:Purine Nucleotides; D011687:Purines