Synthesis and insecticidal activity of spinosyn analogs functionally altered at the 2'-,3'- and 4'-positions of the rhamnose moiety.
In an effort to increase the insecticidal activity of the spinosyn family of naturally occurring macrolides, the 2'-, 3'- and 4'-O-desmethyl-O-acetyl analogs and the 2'-, 3'-, and 4'-O-desmethoxy analogs have been synthesized. These analogs were prepared synthetically from the minor spinosyn factors H, J, K, L and Q either via direct acylation of the corresponding factor or deoxygenation of an intermediate xanthate. The acylated analogs were all more potent insecticides against Heliothis virescens larvae than their respective parent factors, but not as potent as spinosyns A or D. The deoxy analogs were also more potent insecticides than their respective parent factors. The 2'-desmethoxy analogs showed, for the first time, analogs with insecticidal potency against H. virescens greater than that of spinosyns A and D, indicating that polarity is not well tolerated in the rhamnose moiety of spinosyn A.
Creemer
L C
LC
Elanco Animal Health, Research and Development, Greenfield, Indiana 46140, USA.
Kirst
H A
HA
Paschal
J W
JW
Worden
T V
TV
D000818:Animals; D000900:Anti-Bacterial Agents / Q000737:chemistry* / Q000494:pharmacology; D004353:Drug Evaluation, Preclinical; D007306:Insecticides / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology*; D007814:Larva / Q000187:drug effects; D018942:Macrolides; D009036:Moths / Q000187:drug effects; D012210:Rhamnose / Q000737:chemistry; D013329:Structure-Activity Relationship
C408425:2'-desmethoxy spinosyn D; C408423:3'-desmethoxy spinosyn D; D000900:Anti-Bacterial Agents; D007306:Insecticides; D018942:Macrolides; C114883:spinosyn A; C114884:spinosyn D; C408427:spinosyn H; C408428:spinosyn J; C408426:spinosyn K; D012210:Rhamnose