cis-gigantrionenin and 4-acetyl gigantetrocin A, two new bioactive annonaceous acetogenins from Goniothalamus giganteus, and the stereochemistries of acetogenin 1,2,5-triols.

Using activity-directed fractionation, two new bioactive acetogenins, cis-gigantrionenin (1) and 4-acetyl gigantetrocin A (2), have been isolated from the bark of Goniothalamus giganteus (Annonaceae). Compound 1 has a cis-mono-THF ring with one flanking hydroxyl and possesses a cis-double bond at C-21/22 of the aliphatic chain; it represents only the second example of the cis-mono-THF ring annonaceous acetogenins having one flanking hydroxyl. Compound 2 has a trans-mono-THF ring with one flanking hydroxyl, but it possesses a mono-acetyl group at the 4-OH position; it represents only the second natural example of the acetylated annonaceous acetogenins; the first acetogenin reported, uvaricin, was mono-acetylated at the 24-OH. The stereochemistries of 1 and 2 were determined by the advanced Mosher ester method. In addition, the absolute stereochemistries of gigantriocin (3), gigantrionenin (4), and giganenin (5) were determined by the advanced Mosher ester method and by circular dichroism (CD). The stereochemistries of the 7,8-diols in murihexocins A (6) and B (7) were determined to have the S,S-configurations, respectively.