The synthesis of various types of optically active alpha-(allenylsilane-containing)glycines via a chirality-transferring ester-enolate Claisen rearrangement of alpha-acyloxy-alpha-alkynylsilanes is described. The conversion of the rearranged products into the optically active silicon-free alpha-(allenyl)- and alpha-substituted-alpha-(allenyl)glycines was achieved by the removal of the Me(2)PhSi- or TMS group from the allene terminus. (C) 2010 Elsevier Ltd. All rights reserved.