Reassessing the molecular structures of some previously isolated abietane diterpenoids with a naphthalene moiety and the structure-activity relationship (SAR) of quinone diterpenoids

Crystals of previously described para-naphthoquinone abietane diterpenoids 12,16-dideoxy-aegyptinone B and 12-deoxy-salvipisone were obtained from Zhumeria majdae Rech.f. & Wendelbo. However, single-crystal X-ray diffraction analysis followed by reinterpretation of their NMR data revealed that their structures require revision, and they should be revised to the two ortho-naphthoquinones, zhumerianone C and aethiopinone, respectively. Interestingly, a further search through literature revealed that there were more of such cases, in which differentiation between the ortho-/para-orientation had not been carried out correctly in the structure elucidation of naphthalene containing abietane diterpenoids. Therefore, in the current study, we pointed out some 1D and 2D NMR generalizations that would help the unambiguous deduction of the ortho-/para-orientation of naphthalene containing abietanes and revised the structure of some previously described compounds accordingly. Based on these generalizations, structures of sibiriquinones A and B, sahandinone, and sahandone were revised to the known structures 1,2-didehydromiltirone, miltirone, saprorthoquinone, and sahandone B, respectivelyand tebesinone B, arucadiol, and sahandol II were revised to three undescribed structures. It was also proposed that structures of palmitoyl arucadiol and compounds with the salvifolane skeleton need revision. Furthermore, these structure revisions shed light on the structure-activity relationship of the quinone diterpenoids, approving that the ortho-quinone is the critical structural component for cytotoxicity in these compounds.

Automated summary

This study revealed that the structures of two previously described naphthoquinone abietane diterpenoids need revision and proposed some general rules based on 1D and 2D NMR for unambiguous determination of the ortho-/para-orientation of naphthalene containing abietanes. Furthermore, the structures of several other compounds were also revised accordingly, shedding light on the structure-activity relationship of quinone diterpenoids.