Total Synthesis of Millingtonine

Abstract Millingtonine is a glycosidic alkaloid that exists as a pair of pseudo‐enantiomeric diastereomers. Consideration of the likely biosynthetic origins of this unusual natural product has resulted in the development of a seven‐step total synthesis. Results from this synthetic work provide evidence in support of a proposed network of biosynthetic pathways that can account for the formation of several phenylethanoid natural products.