An efficient direct benzylic C-H amination via dehydrogenative-coupling by using an inexpensive catalyst/oxidant (CoBr2/(BuOOBu)-Bu-t-Bu-t) system is described. Various unmodified amides including primary or secondary sulfonamides, carboxamides, and carbamates preformed well with benzylic hydrocarbons with moderate to good yields. (C) 2011 Elsevier Ltd. All rights reserved.