2-and 6-Purinylmagnesium Halides in Dichloromethane: Scope and New Insights into the Solvent Influence on the C-Mg Bond

The generation of positionally stable purin-2- and 6-yl magnesium halides is complicated by the often very rapid isomerization to give the 8-yl Grignards. By conducting the reaction in dichloromethane (DCM), we demonstrated that the anion isomerization can be stopped and these stable purin-2- and 6-yl Grignards react directly with a broad scope of aldehydes in good yields. Furthermore, purine functionalization with ketones has been achieved for the first time in the presence of LaCl3 center dot 2LiCl. Density functional theory calculations offer a possible explanation of the special role played by solvent in this chemistry and show that in DCM the C-Mg bond has a less polar character, whereas in THF it is predominantly ionic and much more basic in nature.

Automated summary

This study demonstrates that the isomerization of purin-2- and 6-yl Grignards to 8-yl Grignards can be stopped by conducting the reaction in dichloromethane (DCM), allowing direct reactions with various aldehydes. In addition, functionalization of purine with ketones has been achieved with the presence of LaCl3·2LiCl. Density functional theory calculations provide an explanation for the role of solvent in this chemistry, indicating that the polarity of the C-Mg bond is influenced by the solvent.