B(C6 F5 )3 -Catalyzed Regioselective Ring Opening of Cyclic Amines with Hydrosilanes.

ABSTRACT

Opening the ring of cyclic amines by regioselective fission of one of the carbon-nitrogen bonds greatly expands the repertoire of available nitrogen-containing skeletons. Unlike approaches starting from cyclic tertiary amines, methods that can directly open secondary amines are still scarce. The present work discloses an efficient reductive ring opening of either of these cyclic amines using PhSiH3 under B(C6 F5 )3 catalysis. By this, the direct transformation of unstrained cyclic amines into the corresponding acyclic amines is achieved in a simple one-pot operation. A stepwise mechanism proceeding through the intermediacy of silylammonium ions followed by reductive cleavage of a carbon-nitrogen bond was experimentally verified.