Enantio- and Diastereoswitchable C-H Arylation of Methylene Groups in Cycloalkanes.

A complementary set of chiral N,N-ligands enables the Pd-catalyzed β-C-H arylation of unbiased internal methylene groups in good yield and with high levels of enantio- and diastereoinduction. Both the dia- and enantioselectivity can be reversed, thus allowing the selective arylation of any of the four β-C-H bonds in cycloalkanecarboxamides of various ring sizes. The method is applicable to a broad range of aryl iodides with electron-withdrawing and -donating substituents in the o-, m-, or p-position.