Identification of (S,S)-γ-glutamyl-(cis-S-1-propenyl)thioglycine, a naturally occurring norcysteine derivative, from the Chinese vegetable Toona sinensis.

Extracts of Toona sinensis shoots were studied to identify the precursors of volatile sulfur-containing flavor molecules. T. sinensis was found to contain new compounds (S,S)-γ-glutamyl-(cis-S-1-propenyl)thioglycine, 1, (S,S)-γ-glutamyl-(trans-S-1-propenyl)thioglycine, 2, and γ-glutamyl-(cis-S-1-propenyl)-cysteine, 3. The structures of these compounds were determined by interpretation of multistage mass spectrometric (MS(n)), 1D, and 2D NMR data. The absolute configuration of 1 was established by comparison of experimental with computed infrared and vibrational circular dichroism spectra. Because of the flexibility of the molecule and the novelty of the structure, the configuration was further confirmed by X-ray crystallography. Compounds 1 and 2 are the first examples of norcysteine-containing metabolites reported from nature. They may release thiols via cleavage of the amide bond by proteases, followed by spontaneous decomposition of the resulting unstable alk(en)yl norcysteine moiety.