Selective functionalization of sp(3) C-H bonds adjacent to nitrogen using (diacetoxyiodo)benzene (DIB)

A PhI(OAc)(2) mediated selective functionalization of sp(3) C-H bonds adjacent to a nitrogen atom has been reported. When piperidine derivates were used, direct diacetoxylation of alpha and beta sp(3) C-H adjacent to a nitrogen atom were observed to afford various cis-2,3-diacetoxylated piperidines. On the other hand, tetrahydroisoquinoline derivatives gave various alpha-C-H functionalized products in the presence of PhI(OAc)(2). Nitroalkanes, dialkyl malonates, and beta-keto ester are active participants in this coupling reaction. Meanwhile, alpha-amino nitriles can also be obtained by oxidative coupling of amines with malononitrile.