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Crystal Structures of Dipeptides Derived from the β-Amino Acids (1R,2S)-2-Aminocyclopentanecarboxylic Acid and (1S,2R,3S)-2-Amino-3-methylcyclopentanecarboxylic Acid

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Abstract

Crystals of the dimeric β-peptides 13 and 20, derived from (1R,2S)-2-aminocyclopentanecarboxylic acid and (1S,2R,3S)-2-amino-3-methylcyclopentanecarboxylic acid, respectively, were synthesised and studied by X-ray diffraction in order to establish their solid state secondary structural characteristics. Compound 13 crystallises in the monoclinic space group P 2 1 with cell parameters of a = 5.2682(1) Å, b = 9.1211(2) Å, c = 22.4467(6) Å, β = 91.3855(9)°, V = 1078.29(4) Å3 and Z = 2. Compound 20 crystallizes in the orthorhombic space group P 2 1 2 1 2 1 with cell parameters of a = 5.0968(1) Å, b = 11.5546(2) Å, c = 43.5414(8) Å, V = 2564.22(8) Å3 and Z = 4. In both cases adjacent molecules are linked by a series of N–H···O=C hydrogen bonds to form β-sheet like structures.

Graphical Abstract

The structures of two dipeptides derived from the β-amino acids (1R,2S)-2-aminocyclopentanecarboxylic acid and (1S,2R,3S)-2-amino-3-methylcyclopentanecarboxylic acid have been analysed by X-ray diffraction.

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Notes

  1. It was found that 2,6-di-tert-butylphenol (2,6-DTBP) was not compatible with preparing large quantities (>10 g) of the prerequisite β-amino ester in the lithium amide conjugate addition step. Thus, an alternative, scalable procedure was developed using 2-pyridone to quench the lithium β-amino enolate which produced a 97:3 mixture of C(2)-epimeric β-amino esters. For other diastereoselective protonations of lithium β-amino enolates with 2-pyridone from our laboratory, see Refs. [45–47].

  2. β-Amino ester (1R,2S)-11 was converted to the corresponding (R)- and (RS)-MTPA derivatives (Mosher’s amides) and was determined to be >98% ee by both 1H and 19F NMR spectroscopic analyses. See Refs. [48–50].

  3. β-Amino ester (1S,2R,3S)-17 was converted to the corresponding (R)- and (RS)-MTPA derivatives (Mosher’s amides) and was determined to be >98% ee by both 1H and 19F NMR spectroscopic analyses. See Refs. [48–50].

  4. The structures of 13 and ent-20 were overlaid using the Chem-3D structure mapping function.

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Authors and Affiliations

  1. Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK

    Elin Abraham, Stephen G. Davies, Paul M. Roberts, Amber L. Thompson & James E. Thomson

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  1. Elin Abraham
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  2. Stephen G. Davies
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  3. Paul M. Roberts
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  4. Amber L. Thompson
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Correspondence to Stephen G. Davies.

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Abraham, E., Davies, S.G., Roberts, P.M. et al. Crystal Structures of Dipeptides Derived from the β-Amino Acids (1R,2S)-2-Aminocyclopentanecarboxylic Acid and (1S,2R,3S)-2-Amino-3-methylcyclopentanecarboxylic Acid. J Chem Crystallogr 41, 1722–1728 (2011). https://doi.org/10.1007/s10870-011-0164-x

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