Forosamine at the 17-position of spinosyns A and D was hydrolyzed under mild acidic conditions to give the corresponding 17-pseudoaglycones. The tri-O-methylrhamnose at the 9-position of the 17-pseudoaglycone of spinosyn A was hydrolyzed under more vigorous acidic conditions to give the aglycone of spinosyn A. However, these conditions led to decomposition of the 17-pseudoaglycone of spinosyn D, presumably due to more facile protonation of the 5,6-double bond to produce a tertiary carbonium ion which undergoes further rearrangements. Spinosyns J and L (3'-O-demethyl spinosyn A and D, respectively) obtained from fermentation of biosynthetically-blocked mutant strains of Saccharopolyspora spinosa, were oxidized to give the corresponding 3'-keto-derivatives and the resultant keto-sugars were then beta-eliminated under basic conditions to give the 9-pseudoaglycones of spinosyns A and D respectively. Forosamine at the 17-position of the 9-pseudoaglycone of spinosyn D was then readily hydrolyzed to yield the aglycone of spinosyn D.

中文翻译：

---

刺糖多孢菌素A和刺糖多孢菌素D分别转化成它们的9-和17-伪糖苷配基和它们的苷元。

在弱酸性条件下，将多杀菌素A和D的17位上的Forosamine水解，得到相应的17-pseudoaglycones。在更剧烈的酸性条件下，将多杀菌素A的17-伪糖苷配基的9位三-O-甲基鼠李糖水解，得到了多杀菌素A的糖苷配基。然而，这些条件导致多杀菌素D的17-伪糖苷配基分解，据推测是由于5，6-双键的质子化作用更容易产生叔碳鎓离子，该碳鎓离子经历了进一步的重排。从生物合成受阻的棘糖多孢菌突变菌株的发酵中得到的刺糖多孢菌素J和L（分别为3'-O-去甲基刺糖多孢菌素A和D）被氧化，得到相应的3' 然后在碱性条件下将β-酮衍生物和所得的酮糖β-消除，分别得到多杀菌素A和D的9-伪糖苷配基。然后容易地水解多杀菌素D的9-伪糖苷配基的17-位的甲酚胺，得到多杀菌素D的糖苷配基。