Total synthesis of (-)-stellettamide B and determination of its absolute stereochemistry.

[figure: see text] The first total synthesis of (-)-stellettamide B has been achieved by a sequence based on amide coupling of the chiral 1-(aminomethyl)-indolizidine fragment, prepared by TiCl4-mediated asymmetric allylation of the tricyclic N-acyl-N,O-acetal, with the chiral trienoic acid fragment. This synthesis led to revision of the published relative stereochemistry of the natural product and established its absolute stereochemistry to be 1S,4S,8aR,6"R.