Conversion of (S)-allethrolone to pyrethrin I, jasmolin I, cinerin I, and [propenyl-3-13C]- and [propenyl-3-14C]-(S)-bioallethrin

Ando, Tetsu; Casida, John E.

doi:10.1021/jf00115a035

Cited by 6 publications

(7 citation statements)

References 10 publications

(16 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…( S )- 12 : Pale yellow oil; [ α ] D 17 + 33.7 ( c 1.39, CHCl 3 ) [lit . [ α ] D 23 + 29.2 ( c 1.7, CHCl 3 )].…”

Section: Methodsmentioning

confidence: 99%

“…Because of the structural resemblance of pyrethrin families, practical separation of pure ingredients from the natural mixture products is virtually impossible, even using recent elaborate techniques. In 1983, Casida and Ando disclosed the first synthetic approach and structure confirmation of “chiral” pyrethrin I based on the analytical data of 90 MHz 1 H NMR spectra and optical rotations . They used the starting ( S )-4-hydroxy-3-methyl-2-(allyl)cyclopent-2-en-1-one precursor with unknown chemical and optical purities that was gifted from a certain company.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Total Syntheses of All Six Chiral Natural Pyrethrins: Accurate Determination of the Physical Properties, Their Insecticidal Activities, and Evaluation of Synthetic Methods

et al. 2020

View full text Add to dashboard Cite

Chiral total syntheses of all six insecticidal natural pyrethrins (three pyrethrin I and three pyrethrin II compounds) contained in the chrysanthemum (pyrethrum) flower were performed. Three common alcohol components [(S)-cinerolone, (S)-jasmololone, and (S)-pyrethrolone] were synthesized: (i) straightforward Sonogashira-type cross-couplings using available (S)-4-hydroxy-3-methyl-2-(2-propynyl)cyclopent-2-en-1-ones (the prallethrin alcohol) for (S)-cinerolone (overall 52% yield, 98% ee) and (S)-pyrethrolone (overall 54% yield, 98% ee) and (ii) traditional decarboxylative-aldol condensation and lipase-catalyzed optical resolution for (S)-jasmololone (overall 16% yield, 96% ee). Two counter acid segments [(1R,3R)-chrysanthemic acid (A) and (1R,3R)-second chrysanthemic acid precursor (B)] were prepared: (i) C(1) epimerization of ethyl (±)-chrysanthemates and optical resolution using (S)-naphthylethylamine to afford A (96% ee) and (ii) concise derivatization of A to B (96% ee). All six pyrethrin esters (cinerin I/II, jasmolin I/II, and pyrethrin I/II) were successfully synthesized utilizing an accessible esterification reagent (TsCl/N-methylimidazole). To investigate the stereostructure–activity relationship, all four chiral stereoisomers of cinerin I were synthesized. Three alternative syntheses of (±)-jasmololone were investigated (methods utilizing Piancatelli rearrangement, furan transformation, and 1-nitropropene transformation). Insecticidal activity assay (KD50 and IC50) against the common mosquito (Culex pipiens pallens) revealed that (i) pyrethrin I > pyrethrin II, (ii) pyrethrin I (II) > cinerin I (II) ≫ jasmolin I (II), and (iii) “natural” cinerin I ≫ three “unnatural” cinerin I compounds (apparent chiral discrimination).

show abstract

“…( S )- 12 : Pale yellow oil; [ α ] D 17 + 33.7 ( c 1.39, CHCl 3 ) [lit . [ α ] D 23 + 29.2 ( c 1.7, CHCl 3 )].…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Total Syntheses of All Six Chiral Natural Pyrethrins: Accurate Determination of the Physical Properties, Their Insecticidal Activities, and Evaluation of Synthetic Methods

et al. 2020

View full text Add to dashboard Cite

show abstract

“…According to Todd et al (2003), pyrethrins are non-volatile at ambient temperatures (WHO, 1975), with low vapor pressures and low Henry's constants, and large octanol/water coefficients (Table 1). Synthesis of pyrethrin I, jasmolin I, and cinerin I from (S)-Allethrolone has been reported by Ando and Casida (1983).…”

Section: Chemical Propertiesmentioning

confidence: 99%

Control of Dark-winged Fungus Gnats (Lycoriella ingenua) using Mist Fogger with Natural Pyrethrum (Tanacetum cinerariifolium)

Yoon¹,

Chae²,

Kim³

et al. 2017

KJPS

View full text Add to dashboard Cite

“…Interestingly, the elution order of the (Z)-and (E)-isomers in this HPLC system was different from that by GLC and Si0 2 -AgN0 3 column. 4 ) HPLC analyses for these mixtures were also examined with other polar columns (Nucleosil N0 2 and N(CH 3 )2) and another solvent system (2-propanol in n-hexane). Although the elution order was the same for every combination, the ability to separate the stereoisomers was different to various extents.…”

Section: 'Z)- (1s2'e)-and (1r2'e)-isomers Of Pyrethrin I ((A)-i)mentioning

confidence: 99%

“…4 ) This mixture, which gave only one spot· on a silica gel TLC plate, was analyzed on a Nuc1eosil 5CN HPLC column (8 mm i.d. x 20 cm) with 1% tetrahydrofuran (THF) in n-hexane.…”

mentioning

confidence: 99%

High Performance Liquid Chromatographic Separation of the Stereoisomers of Natural Pyrethrins and Related Compounds

Ando

Kurotsu

Uchiyama

1986

Agricultural and Biological Chemistry

Self Cite

View full text Add to dashboard Cite

Conversion of (S)-allethrolone to pyrethrin I, jasmolin I, cinerin I, and [propenyl-3-13C]- and [propenyl-3-14C]-(S)-bioallethrin

Cited by 6 publications

References 10 publications

Total Syntheses of All Six Chiral Natural Pyrethrins: Accurate Determination of the Physical Properties, Their Insecticidal Activities, and Evaluation of Synthetic Methods

Total Syntheses of All Six Chiral Natural Pyrethrins: Accurate Determination of the Physical Properties, Their Insecticidal Activities, and Evaluation of Synthetic Methods

Control of Dark-winged Fungus Gnats (Lycoriella ingenua) using Mist Fogger with Natural Pyrethrum (Tanacetum cinerariifolium)

High Performance Liquid Chromatographic Separation of the Stereoisomers of Natural Pyrethrins and Related Compounds

Contact Info

Product

Resources

About