8-(Arylmethyl)berbines are conveniently obtained through a Stevens rearrangement of the corresponding N-arylmethylberbinium salts with sodium methylsulfinylmethylide in DMSO. This procedure has provided two new nonnatural 8-benzylcanadines stereoselectively, without competition from the Hofmann elimination. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).