Synthesis and Insecticidal Activity of Spinosyns with C9-<i>O</i>-Benzyl Bioisosteres in Place of the 2′,3′,4′-Tri-<i>O</i>-methyl Rhamnose

Oliver, M. Paige; Crouse, Gary D.; Demeter, David A.; Sparks, Thomas C.

doi:10.1021/acs.jafc.5b01987

Cited by 9 publications

(6 citation statements)

References 37 publications

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“…The diet bioassays were run as described previously 23 using second instar larvae of S. exigua and Heliothis zea (corn earworm), with 16 larvae per dose, 4–5 doses, replicated two to three times. The Drosophila bioassays were run using adult D. melanogaster as described previously 9 with 10–16 flies per dose and 4–5 doses replaced on four separate occasions.…”

Section: Methodsmentioning

confidence: 99%

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De Novo Design of Potent, Insecticidal Synthetic Mimics of the Spinosyn Macrolide Natural Products

Crouse¹,

Demeter²,

Samaritoni

et al. 2018

Sci Rep

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New insect pest control agents are needed to meet the demands to feed an expanding global population, to address the desire for more environmentally-friendly insecticide tools, and to fill the loss of control options in some crop-pest complexes due to development of insecticide resistance. The spinosyns are a highly effective class of naturally occurring, fermentation derived insecticides, possessing a very favorable environmental profile. Chemically, the spinosyns are composed of a large complex macrolide tetracycle coupled to two sugars. As a means to further exploit this novel class of natural product-based insecticides, molecular modeling studies coupled with bioactivity-directed chemical modifications were used to define a less complex, synthetically accessible replacement for the spinosyn tetracycle. These studies lead to the discovery of highly insecticidal analogs, possessing a simple tri-aryl ring system as a replacement for the complex macrolide tetracycle.

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Section: Methodsmentioning

confidence: 99%

“…2′, 3′, 4′-Tri- O -methyl-L-rhamnopyranoside was obtained by hydrolysis of spinosad under previously described conditions 23 . All reactions were executed under N 2 in dried glassware.…”

Section: Methodsmentioning

confidence: 99%

De Novo Design of Potent, Insecticidal Synthetic Mimics of the Spinosyn Macrolide Natural Products

Crouse¹,

Demeter²,

Samaritoni

et al. 2018

Sci Rep

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“…It is considered that pesticides originating from plant secondary metabolites may result in less or slower resistance development and lower pollution 18 19 . Recently, discovery of new insecticidal components directly from plant secondary metabolites, or by using them as the lead-compounds for structural modifications has been one of the important procedures for research and development of new pesticides 20 21 22 23 .…”

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confidence: 99%

Insight into 2α-Chloro-2′(2′,6′)-(Di)Halogenopicropodophyllotoxins Reacting with Carboxylic Acids Mediated by BF3·Et2O

Fan

Zhi

Che

et al. 2015

Sci Rep

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Stereospecific nucleophilic substitution at the C-4α position of 2α-chloro-2′(2′,6′)-(di)halogenopicropodophyllotoxin derivatives with carboxylic acids mediated by BF3·Et2O was described. Interestingly, this stereoselective products were completely controlled by the reaction time. That is, if the reaction time was prolonged to 24.5–31 h, the resulting compounds were all transformed into the unusual C-ring aromatization products. Additionally, it demonstrated that BF3·Et2O and reaction temperature were the important factors for C-ring aromatization, and AlCl3 could be substituted for BF3·Et2O as a lewis acid for C-ring aromatization. Halogenation of E-ring of 2β-chloropodophyllotoxins with NCS or NBS also led to the same C-ring aromatization compounds. Especially compounds 5c, 6g and 7b exhibited insecticidal activity equal to that of toosendanin.

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“…Colored areas highlight specific changes to the spinosyn structure. Information summarized from 10,16,19–22 …”

Section: Introductionmentioning

confidence: 99%

The spinosyns, spinosad, spinetoram, and synthetic spinosyn mimics ‐ discovery, exploration, and evolution of a natural product chemistry and the impact of computational tools

Sparks¹,

Crouse

Benkő

et al. 2020

Pest Management Science

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Natural products (NPs) have long been a source of insecticidal crop protection products. Like many macrolide NPs, the spinosyns originated from a soil inhibiting microorganism (Saccharopolyspora spinosa). More than 20 years after initial registration, the spinosyns remain a unique class of NP‐based insect control products that presently encompass two insecticidal active ingredients, spinosad, a naturally occurring mixture of spinosyns, and spinetoram, a semi‐synthetic spinosyn product. The exploration and exploitation of the spinosyns has, unusually, been tied to an array of computational tools including artificial intelligence (AI)‐based quantitative structure activity relationship (QSAR) and most recently computer‐aided modeling and design (CAMD). The AI‐based QSAR directly lead to the discovery of spinetoram, while the CAMD studies have recently resulted in the discovery and building of a series of synthetic spinosyn mimics. The most recent of these synthetic spinosyn mimics show promise as insecticides targeting lepidopteran insect pests as demonstrated by field studies wherein the efficacy has been shown to be comparable to spinosad and spinetoram. These and a range of other aspects related to the exploration of the spinosyns over the past 30 years are reviewed herein. © 2020 Society of Chemical Industry

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Synthesis and Insecticidal Activity of Spinosyns with C9-O-Benzyl Bioisosteres in Place of the 2′,3′,4′-Tri-O-methyl Rhamnose

Cited by 9 publications

References 37 publications

De Novo Design of Potent, Insecticidal Synthetic Mimics of the Spinosyn Macrolide Natural Products

De Novo Design of Potent, Insecticidal Synthetic Mimics of the Spinosyn Macrolide Natural Products

Insight into 2α-Chloro-2′(2′,6′)-(Di)Halogenopicropodophyllotoxins Reacting with Carboxylic Acids Mediated by BF3·Et2O

The spinosyns, spinosad, spinetoram, and synthetic spinosyn mimics ‐ discovery, exploration, and evolution of a natural product chemistry and the impact of computational tools

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