Epoxychrysanthemates: two-dimensional NMR analyses and stereochemical assignments

Three‐bond 13C1H coupling constants for chrysanthemic acid and phenothrin metabolites: Detection by two‐dimensional long‐range 13C1H J‐resolution spectroscopy

“…Similarly, 3J(C,H) values of 1-2.5 Hz (trans) and 1.5-3.5 Hz (cis) for epoxide rings correspond to 3J(H,H) values of 2-3.5 Hz (trans) and 3-5 Hz (cis), and 3J(C,H) values of 6-12.5 Hz (trans) and 3-8.5 Hz (cis) for C=C bonds correspond to 3J(H,H) values of 12-18 Hz (trans) and 6-12 Hz (cis). 3 The 3J(C,H) values for the analogous groupings in 1, 2 and 5 (Table 1) H) values with H-3 than the trans-carbons (i.e. C-6 and C-5, respectively).…”

Metabolism of the Insecticide Metofluthrin in Cabbage (Brassica oleracea)

“…Sauveplane et al reported the CYP derived from Arabidopsis (Arabidopsis thaliana), which was heterologously expressed in yeast (Saccharomyces cerevisiae), showed highly selective conversion of ( Z )-configured unsaturated fatty acids to mono- or di- cis -epoxide . Incidentally, Ando et al extensively studied the configuration of the epoxy chrysanthemate derivatives of ( S )-bioallethrin and phenothrin produced by mouse microsomal CYP. − They have clarified that the oxygen atom was inserted into the propenyl double bond from the si face to produce the 7,8-epoxy derivative and its configuration at C7 carbon, the one adjacent to the cyclopropane ring, was R and S from selective oxidation of trans - and cis -chrysanthemates, respectively. Additionally, epoxy hydrolases, which transform epoxy derivatives into diols, are also reported to be stereoselective.…”

Epoxy and hydroxy derivatives of (S)-bioallethrin and pyrethrins I and II: synthesis and metabolism

“…Column chromatography utilized silica gel 60 (70-230-mesh ASTM; Merck, Darmstadt, Germany) with a solvent gradient of n-hexane to acetone. TLC and HPLC methods were as described previously (Ando et al, 1990). Semiquantitative determinations of pyrethroids and their derivatives were performed by integration of the HPLC peak areas determined at 235 nm. Spectroscopy.…”

“…Semiquantitative determinations of pyrethroids and their derivatives were performed by integration of the HPLC peak areas determined at 235 nm. Spectroscopy. NMR spectra were recorded as previously reported (Ando et al, 1990). Chemical ionization GC/MS was accomplished with a Hewlett-Packard 5985 GC/MS system fitted with a SPB5 (Supelco Inc., Bellefonte, PA) (for derivatives of PI and PII) or a DB5 (J&W Scientific, Folsom, CA) (for derivatives of A) fused silica capillary column (30 m X 0.25 mm i.d., 0.25-µ film).…”