Structural similarities across 1–15 suggest a highly conserved biosynthesis. Building on this observation, we propose a biosynthetic relationship (Figure 5), in which the aconitates A–F (1–6) are viewed as mono, di, and tri methyl esters of the precursor E-aconitic acid, itself a dehydration product of citric acid. Likewise, metabolites 7–15 can be viewed as adducts between aconitates and an intermediate quinone methide that is generated from 2,3,6-tribromo-4,5-dihydroxybenzyl alcohol, further elaborated by a combination of 1,3-hydride shifts, decarboxylations and oxidations. Although 7a/b, 9a/b, 10–11, and 13 incorporate a single chiral sp3 center, as they do not exhibit measurable optical rotations they are presumed to be racemic, as confirmed for 10 by X-ray crystallography. The absence of double bond migrations (i.e., racemization) during isolation and handling suggests that this racemic character is a function of achiral adduct addition. The proposed biosynthetic relationship informs a possible biomimetic synthesis of 7–15, although, in our hands, synthetic 2,3,6-tribromo-4,5-dihydroxybenzyl alcohol proved stable to both acid and base conditions indicative of a requirement to activate the benzyl alcohol moiety to effect dehydration and the formation of a quinone methide.