A simple, inexpensive, environmentally friendly, and highly efficient benzylation and allylation of 1,3-dicarbonyl compounds with sulfonamides in the presence of Yb(OTf)(3) is described. Yb(OTf)(3) was proved to be a good catalyst for the cleavage of sp(3) carbon-nitrogen bond. Various 1,3-dicarbonyl compounds can couple with a broad range of tosyl-activated benzylic and allylic amines to give diversely functionalized products in good to excellent yields. (C) 2012 Elsevier Ltd. All rights reserved.