The single-crystal X-ray diffraction of a novel alkaloid, stellettamine (15), together with long-range 1H‒13C coupling constants obtained by inverse detection methods, and metal chelation studies have shown that the previously reported regiochemistry of the thiazole moiety of dercitin (1) and four other related alkaloids 2-5 has to be revised. The corrected structures 10–14 are related to, and in one case identical to, those of the kuanoniamines 6–9. © 1992, American Chemical Society. All rights reserved.