Configurationally stable ε-amido-propargylindiums, generated in situ from N-Ts-4-ethynylazetidin-2-ones in the presence of InI, catalytic amounts of Pd­(PPh3)4, and N-methylimidazole or pyridine ligand react with unusual regioselectivity with aromatic and aliphatic aldehydes to afford 2,6-syn- or 2,6-anti-allenediols with excellent central-to-axial chirality transfer and useful levels of acyclic remote 1,5-stereocontrol.

The switch from N-methylimidazole (N-MI) to the Et3N N-ligand efficiently alters diastereoselectivity in Pd(0)/InI-mediated allylations of aldehydes with β-lactam-derived organoindiums. As a result, (3E)-selective allylations and crotylations of a variety of aliphatic and (hetero)­aromatic aldehydes with differently substituted chiral ε-amido-allylindiums were developed. Depending on the relative β-lactam configuration, the reactions occur under kinetic or thermodynamic control, with effective remote 1,5- or 1,4,5-asymmetric induction to afford a diversity of previously unavailable (3E)-2,5-syn-2,6-anti-, (3E)-2,5-anti-2,6-anti-, and (3E)-2,5-anti-2,6-syn-substituted enediols, amino alcohols, and homoallylic alcohols in modest to high yields and with moderate to excellent diastereoselectivity. The effect of the N-ligand as well as β-lactam and aldehyde structures on the yield and stereoselectivity was investigated.