Analyzing the hydrocyanation reaction: chiral HPLC and the synthesis of racemic cyanohydrins

Gerrits, Pieter Jan; Zumbrägel, Friedhelm; Marcus, Jan

doi:10.1016/s0040-4020(01)00819-5

Cited by 12 publications

(2 citation statements)

References 34 publications

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“…Determination of Conversion and %ee. The methods for direct (e.g., HPLC with chiral column) and indirect (e.g., formation of derivatives) determination of conversion from aldehydes to cyanohydrins and %ee of cyanohydrins are available in the literature (21,27). Indirect determination of %ee of 6-MONCH(OH)CN by synthesis of a derivative with (1R,2S,5R)-(-)-menthylchloroformate and then 1 H NMR was known to determine absolute configuration of R and S isomers (21).…”

Section: Resultsmentioning

confidence: 99%

Development of Optically Pure Pyrethroid-Like Fluorescent Substrates for Carboxylesterases

Huang

Stok

Stoutamire

et al. 2005

Chem. Res. Toxicol.

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Pyrethroids are now the world's most extensively used insecticides. One of the common metabolic routes of pyrethroid insecticides in living systems is hydrolysis by carboxylesterases, and this hydrolysis may be stereospecific since most pyrethroid insecticides have chiral centers. In previous studies, pyrethroid-like fluorescent substrates have been shown to be hydrolyzed in a fashion similar to actual pyrethroids. It is important to synthesize the stereoisomers of pyrethroid-like fluorescent substrates to study the stereointeraction between carboxylesterases and these substrates. In this study, an effective synthetic method for preparing optically enriched (R)- and (S)-α-2-hydroxy-2-(6-methoxy-2-naphthyl)acetonitrile was developed. With this alcohol, an efficient synthetic route for preparation of optically pure cypermethrin and fenvalerate analogues was provided. Identification of these stereoisomers was determined based on GC, HPLC, 1H NMR, and X-ray crystallography. In addition, stereointeraction between carboxylesterases and chiral fluorescent substrates indicated that (i) stereospecificity of recombinant mouse liver carboxylesterases (NCBI accession nos. BAC36707 and NM_133960) varied significantly (up to 300-fold difference) with different stereoisomers of cypermethrin and fenvalerate analogues; (ii) on the basis of V max, the sensitivity of this analytical method, using a single stereoisomer of cypermethrin analogues instead of a mixture of eight stereosiomers, could be enhanced by 4−6 times for detection of these carboxylesterases; and (iii) possible usage of these carboxylesterases for chiral synthesis is discussed.

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Section: Resultsmentioning

confidence: 99%

Development of Optically Pure Pyrethroid-Like Fluorescent Substrates for Carboxylesterases

Huang

Stok

Stoutamire

et al. 2005

Chem. Res. Toxicol.

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“…150 µl) was taken and purged to dryness before adding milli-Q water (10 ml) for testing neat with the A. manglesii bioassay. The active fraction (fraction 12) was evaporated to dryness (9.4 mg) and analysed by 1 H, 13 45 and mandelonitrile (6) 46 were prepared according to literature procedures. Synthesis of the (R)-and (S)-enantiomers of 2 were achieved from (S)-and (R)-glyceraldehyde 21,22 respectively following the method of Chelucci et al 23 ( Enantioselective HPLC.…”

Section: A Manglesii Bioassaymentioning

confidence: 99%

Burning vegetation produces cyanohydrins that liberate cyanide and stimulate seed germination

et al. 2011

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Cyanide is well known for its toxicity towards living organisms. many plants use cyanide as a defensive agent against herbivores, releasing it through the enzymatic hydrolysis of endogenous cyanogenic compounds. At low concentrations, cyanide has been proposed to have a regulatory role in many plant processes including stimulation of seed germination. However, no ecological role for cyanide in seed germination has been established. In the present study, we show that burning plant material produces the cyanohydrin, glyceronitrile. We also show that, in the presence of water, glyceronitrile is slowly hydrolysed to release cyanide that stimulates seed germination of a diverse range of fire-responsive species from different continents. We propose that glyceronitrile serves as an ecological store for cyanide and is an important cue for stimulating seed germination and landscape regeneration after fires.

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Chiral Synthesis of Pharmaceutical Intermediates Using Oxynitrilases

Lin

2009

Biocatalysis for the Pharmaceutical Industry

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Analyzing the hydrocyanation reaction: chiral HPLC and the synthesis of racemic cyanohydrins

Cited by 12 publications

References 34 publications

Development of Optically Pure Pyrethroid-Like Fluorescent Substrates for Carboxylesterases

Development of Optically Pure Pyrethroid-Like Fluorescent Substrates for Carboxylesterases

Burning vegetation produces cyanohydrins that liberate cyanide and stimulate seed germination

Chiral Synthesis of Pharmaceutical Intermediates Using Oxynitrilases

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