Dimethylaziridine carboxylic acid

Last updated
Dimethylaziridine carboxylic acid
Dimethyl aziridine carboxylic acid.svg
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
  • InChI=1S/C5H9NO2/c1-5(2)3(6-5)4(7)8/h3,6H,1-2H3,(H,7,8)
    Key: LQNRQHXPYZSWHH-UHFFFAOYSA-N
  • (2S):InChI=1S/C5H9NO2/c1-5(2)3(6-5)4(7)8/h3,6H,1-2H3,(H,7,8)/t3-/m1/s1
    Key: LQNRQHXPYZSWHH-GSVOUGTGSA-N
  • CC1(C(N1)C(=O)O)C
  • (2S):CC1([C@H](N1)C(=O)O)C
Properties
C5H9NO2
Molar mass 115.13 g·mol −1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Dimethylaziridine carboxylic acid or pleurocybellaziridin is a naturally occurring non-proteinogenic amino acid that contains the unusual aziridine ring. It is found in the potentially deadly angel wing mushroom.

Contents

Occurrence

Pleurocybella porrigens Pleurocybella porrigens 177980 cropped.jpg
Pleurocybella porrigens

Dimethylaziridine carboxylic acid occurs in enantiopure 2S form in the mushroom Pleurocybella porrigens. The compound is very unstable, but can be isolated as an ester of benzhydrol by reacting the methanol extract of Pleurocybella mushrooms with diphenyldiazomethane. In one case, 23 mg of the ester derivative was isolated from 4 g of freeze-dried mushrooms. [1] The compound is synthesized by members of the fungal kingdom as an offshoot of valine biosynthesis, involving an oxygenase that uses α-ketoglutaric acid and iron (II) ions as cofactors. [2]

Synthesis

The synthesis starts with a cyclic BOC protected derivative of serine known as Garner's ester. In the first step, this compound is reacted with methylmagnesium bromide to form a tertiary alcohol. The ring is then opened up with pyridinium tosylate. The hydroxyl group of the ring opened compound is then oxidized to a carboxylic acid using a mix of TEMPO, sodium chlorite, and PIDA dissolved in acetonitrile. This carboxylic acid is then reacted with diazomethane in diethyl ether to form the methyl ester. The BOC group is removed by reaction with gaseous hydrogen chloride in methanol, and the amino group is protected with 2,4-dinitrobenzenesulfonyl chloride using 2,6-lutidine as the base. The aziridine ring system of the amino acid is formed by reaction with diisopropyl azodicarboxylate and triphenylphosphane (A type of Mitsunobu reaction). All protecting groups are then removed by reaction with propylamine in dichloromethane to give the final product. [1]

Toxicology

The genus Pleurocybella occurs worldwide in temperate climates and Pleurocybella porrigens was a particularly popular edible mushroom in Japan. In 2004, 17 people died there after eating the mushrooms. The affected individuals mainly suffered from chronic kidney failure, which explains why the mushrooms can often be consumed without any recognizable health consequences. The toxicity is attributed to dimethylaziridine carboxylic acid, which damages oligodendrocytes and can thus cause encephalopathy. [1]

References

  1. 1 2 3 Toshiyuki Wakimoto, Tomohiro Asakawa, Saeko Akahoshi, Tomohiro Suzuki, Kaoru Nagai, Hirokazu Kawagishi, Toshiyuki Kan (February 2011), "Proof of the Existence of an Unstable Amino Acid: Pleurocybellaziridine in Pleurocybella porrigens", Angewandte Chemie, vol. 123, no. 5, pp. 1200–1202, Bibcode:2011AngCh.123.1200W, doi:10.1002/ange.201004646 {{citation}}: CS1 maint: multiple names: authors list (link)
  2. ↑ Reito Bunno, Takayoshi Awakawa, Takahiro Mori, Ikuro Abe (2021-07-12), "Aziridine Formation by a Fe II /α-Ketoglutarate Dependent Oxygenase and 2-Aminoisobutyrate Biosynthesis in Fungi", Angewandte Chemie International Edition, vol. 60, no. 29, pp. 15827–15831, doi:10.1002/anie.202104644, PMID   33973699 {{citation}}: CS1 maint: multiple names: authors list (link)
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