Regioselective α-Cyanation of Unprotected Alicyclic Amines.

Secondary alicyclic amines are converted to α-aminonitriles via addition of TMSCN to their corresponding imines, intermediates that are produced in situ via the oxidation of amine-derived lithium amides with simple ketone oxidants. Amines with an existing α-substituent undergo regioselective α'-cyanation even if the C-H bonds at that site are less activated. Amine α-arylation can be combined with α'-cyanation to generate difunctionalized products in a single operation.

C-H Bond Functionalization of Amines: A Graphical Overview of Diverse Methods.

This Graphical Review provides a concise overview of the manifold and mechanistically diverse methods that enable the functionalization of sp C-H bonds in amines and their derivatives.

α,α'-C-H Bond Difunctionalization of Unprotected Alicyclic Amines.

A simple one-pot procedure enables the sequential, regioselective, and diastereoselective introduction of the same or two different substituents to the α- and α'-positions of unprotected azacycles. Aryl, alkyl, and alkenyl substituents are introduced via their corresponding organolithium compounds. The scope of this transformation includes pyrrolidines, piperidines, azepanes, and piperazines.