The synthesis of (±) -9-demethylprotoemetinol [(±) -3d] was accomplished by LiAlH₄ reduction of the tricyclic ester (±) -5 and subsequent debenzylation of the resulting tricyclic alcohol (±) 10. Acetylation of (±) -3d with acetic anhydride and pyridine gave the diacetate (±) -11. The same sequence of reactions starting with (-) -5 afforded (-) -9-demethylprotoernetinol [(-) -3d] and the diacetate (-) -11 through (-) -10. Parallel synthetic routes starting with the isomeric tricyclic esters (±) -9 and (-) -9 produced (±) -and (-) -10-demethylprotoemetinols [(±) -4d and (-) -4d] and the corresponding diacetates [(±) -13 and (-) -13] through (±) -12 and (-) -12, respectively. The correctness of the structure and absolute stereochemistry of an Alangium alkaloid inferred to be 10-demethylprotoemetinol was confirmed by a direct comparison of its diacetate with synthetic (-) -13.