Spontaneous conversions of glutamine, histidine and arginine into α-hydroxycarboxylates with NH4VO3 or V2O5

Abstract

Glutamine gets transformed to 2-hydroxy-5-oxoproline with NH₄VO₃ in a neutral solution as a product of 2,2′-bipyridine oxidovanadium(V) 2-hydroxy-5-oxoproline [V^V₂O₃(hop)₂(bpy)₂]·7H₂O [1, H₂hop = 2-hydroxy-5-oxoproline] with yields of 65.6%. Similarly, histidine and arginine are converted into the corresponding α-hydroxycarboxylates as 2,2′-bipyridine oxidovanadium(IV) 3-(1H-imidazolyl-5-yl)-2-hydroxyacrylate [V^IV₂O₂(imha)₂(bpy)₂]·bpy [2, H₂imha = 3-(1H-imidazolyl-5-yl)-2-hydroxyacrylic acid] and guanidinium oxidovanadium(V) 1-(aminoiminomethyl)-2-hydroxyproline (CN₃H₆)[V^VO₂(Haimhp)₂]·2H₂O [3, H₂aimhp = 1-(aminoiminomethyl)-2-hydroxyproline] with V₂O₅ in low yields respectively, where an aggregate of oxidovanadium(V) arginine (H₂arg)_n(V^VO₃)_n·½nH₂O (4, Harg = arginine) has been isolated preferentially in an initial experiment for 3. α-Hydroxycarboxylates chelate bidentately with vanadium via α-alkoxy and α-carboxy groups in 1–3, as observed from structural analyses. Their racemizations have been observed after the conversions. There is no coordination in 4 based on solid-state ¹³C NMR spectra, and only strong hydrogen bonds exist in the anion chains (V^VO₃)⁻ and protonated arginines. 1 and 4 were fully characterized by elemental analysis, UV–vis, IR and solid-state ¹³C NMR spectroscopies, TG and X-ray structural analyses, and theoretical bond valence calculations (BVS). The conversions of glutamine, histidine and arginine occur spontaneously in a solution under ambient conditions.