Synthesis of New Amino Acids with a 5-Imino-2,5-dihydro-3-furanyl Substituent­ at the Amino Group

Abstract

Amino acids (glycine, β-alanine, γ-aminobutyric and ε-aminocapronic acids, d,l-valine, and d,l-leucine) react under biomimetic conditions (H₂O, NaOH, pH ˜8.6-9.9, room temperature) smoothly with α,β-acetylenic γ-hydroxyacid nitriles to give a novel family of unnatural amino acids containing a 5-imino-2,5-dihydro-3-furanyl substituent at the amino group, in 61-98% yield. As follows from a single-crystal X-ray analysis of 2-[(5-imino-2,2-dimethyl-2,5-dihydro-3-furanyl)amino]acetic acid, the synthesized amino acids are zwitterions with a protonated imino group in the iminodihydrofuran moiety.

amino acids - acetylenes - nitriles - 2,5-dihydrofurans - nucleophilic addition

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Crystallographic data: monoclinic, space group C2/c, a = 20.712(4) Å, b = 9.194(2) Å, c = 10.712(2) Å, β = 120.52(3)°, V = 1757.2(6) ų, Z = 8, D_calcd = 1.39 g/cm³, reflections with [F ₀ > 4σ(F ₀)] = 1498, parameters refined = 167, R = 0.031. CCDC 628146 (for 11) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif

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