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Structural features of thePip/AzPip couple in the crystalline state: influence of the relative AzPip location in an azadipeptide sequence upon the induced chirality and conformational characteristics

Identifieur interne : 001557 ( Istex/Corpus ); précédent : 001556; suivant : 001558

Structural features of thePip/AzPip couple in the crystalline state: influence of the relative AzPip location in an azadipeptide sequence upon the induced chirality and conformational characteristics

Auteurs : C. Didierjean ; A. Aubry ; F. Wyckaert ; G. Boussard

Source :

RBID : ISTEX:D528F1C3BF73E50267FDCAB7B00616C9682B18E4

English descriptors

Abstract

Abstract: Azapipecolic (AzPip) is a pipecolic (Pip) residue analogue containing a nitrogen atom in place of the CαH group. AzPip was introduced into two reverse dipeptide sequences,Piv‐AzPip‐l‐Ala‐NHiPr I and Boc‐l‐Ala‐AzPip‐NHiPr II in order to evaluate, in the crystalline state, the influence of thel‐Ala‐induced chirality upon the prochiral AzPip residue, and therefore the resulting conformational characteristics, according to the relative position of the AzPip residue. Piv‐dl‐Pip‐NHMe III served as a control derivative for comparison between the properties of the two different heterocycles of Pip and AzPip residues. Piperidine and hexahydropyridazine rings have a few characteristics in common: chair conformation, axial disposition of the C‐terminal backbone substituent and the cisoid form of the N‐terminal tertiary amide function. An almost pure sp3 hybridization state is observed for the substituted nitrogen atom Nα, so that l‐Ala induces an AzPip (R) or (S) chirality when it follows or precedes, respectively, the azaresidue in such a pseudodipeptide sequence. If both I and II compounds present a short NH…N contact between the sp2 tertiary amide nitrogen atom and the NH of the next secondary amide function, whatever the chiral nature of the sequence, the heterochiral azadipeptide I adopts a rather totally extended conformation while the homochiral azadipeptide II is folded by a β‐VI turn‐like structure stabilized by a classical 4→1 intramolecular hydrogen bond.

Url:
DOI: 10.1034/j.1399-3011.2000.00686.x

Links to Exploration step

ISTEX:D528F1C3BF73E50267FDCAB7B00616C9682B18E4

Le document en format XML

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<div type="abstract">Abstract: Azapipecolic (AzPip) is a pipecolic (Pip) residue analogue containing a nitrogen atom in place of the CαH group. AzPip was introduced into two reverse dipeptide sequences,Piv‐AzPip‐l‐Ala‐NHiPr I and Boc‐l‐Ala‐AzPip‐NHiPr II in order to evaluate, in the crystalline state, the influence of thel‐Ala‐induced chirality upon the prochiral AzPip residue, and therefore the resulting conformational characteristics, according to the relative position of the AzPip residue. Piv‐dl‐Pip‐NHMe III served as a control derivative for comparison between the properties of the two different heterocycles of Pip and AzPip residues. Piperidine and hexahydropyridazine rings have a few characteristics in common: chair conformation, axial disposition of the C‐terminal backbone substituent and the cisoid form of the N‐terminal tertiary amide function. An almost pure sp3 hybridization state is observed for the substituted nitrogen atom Nα, so that l‐Ala induces an AzPip (R) or (S) chirality when it follows or precedes, respectively, the azaresidue in such a pseudodipeptide sequence. If both I and II compounds present a short NH…N contact between the sp2 tertiary amide nitrogen atom and the NH of the next secondary amide function, whatever the chiral nature of the sequence, the heterochiral azadipeptide I adopts a rather totally extended conformation while the homochiral azadipeptide II is folded by a β‐VI turn‐like structure stabilized by a classical 4→1 intramolecular hydrogen bond.</div>
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<abstract>Abstract: Azapipecolic (AzPip) is a pipecolic (Pip) residue analogue containing a nitrogen atom in place of the CαH group. AzPip was introduced into two reverse dipeptide sequences,Piv‐AzPip‐l‐Ala‐NHiPr I and Boc‐l‐Ala‐AzPip‐NHiPr II in order to evaluate, in the crystalline state, the influence of thel‐Ala‐induced chirality upon the prochiral AzPip residue, and therefore the resulting conformational characteristics, according to the relative position of the AzPip residue. Piv‐dl‐Pip‐NHMe III served as a control derivative for comparison between the properties of the two different heterocycles of Pip and AzPip residues. Piperidine and hexahydropyridazine rings have a few characteristics in common: chair conformation, axial disposition of the C‐terminal backbone substituent and the cisoid form of the N‐terminal tertiary amide function. An almost pure sp3 hybridization state is observed for the substituted nitrogen atom Nα, so that l‐Ala induces an AzPip (R) or (S) chirality when it follows or precedes, respectively, the azaresidue in such a pseudodipeptide sequence. If both I and II compounds present a short NH…N contact between the sp2 tertiary amide nitrogen atom and the NH of the next secondary amide function, whatever the chiral nature of the sequence, the heterochiral azadipeptide I adopts a rather totally extended conformation while the homochiral azadipeptide II is folded by a β‐VI turn‐like structure stabilized by a classical 4→1 intramolecular hydrogen bond.</abstract>
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Azapipecolic (AzPip) is a pipecolic (Pip) residue analogue containing a nitrogen atom in place of the C
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<hi rend="bold">III</hi>
served as a control derivative for comparison between the properties of the two different heterocycles of Pip and AzPip residues. Piperidine and hexahydropyridazine rings have a few characteristics in common: chair conformation, axial disposition of the C‐terminal backbone substituent and the cisoid form of the N‐terminal tertiary amide function. An almost pure
<hi rend="italic">sp</hi>
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‐Ala induces an AzPip (
<hi rend="italic">R</hi>
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<hi rend="italic">S</hi>
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<hi rend="bold">I</hi>
and
<hi rend="bold">II</hi>
compounds present a short NH…N contact between the
<hi rend="italic">sp</hi>
<hi rend="superscript">2</hi>
tertiary amide nitrogen atom and the NH of the next secondary amide function, whatever the chiral nature of the sequence, the heterochiral azadipeptide
<hi rend="bold">I</hi>
adopts a rather totally extended conformation while the homochiral azadipeptide
<hi rend="bold">II</hi>
is folded by a β‐VI turn‐like structure stabilized by a classical 4→1 intramolecular hydrogen bond.</p>
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G. C. Boussard

<i>LCPM, Groupe ENSIC</i>
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<i>‐nancy. fr</i>
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<p>
<b>Abstract:</b>
Azapipecolic (AzPip) is a pipecolic (Pip) residue analogue containing a nitrogen atom in place of the C
<sup>α</sup>
H group. AzPip was introduced into two reverse dipeptide sequences,Piv‐AzPip‐
<sc>l</sc>
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<b>I</b>
and Boc‐
<sc>l</sc>
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<sc>l</sc>
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<sc>dl</sc>
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<b>III</b>
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<i>sp</i>
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<sup>α</sup>
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<sc>l</sc>
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<i>R</i>
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<i>S</i>
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<b>I</b>
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<b>II</b>
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<i>sp</i>
<sup>2</sup>
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<b>I</b>
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<b>II</b>
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<b>To cite this article:</b>
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<p>
<i>Didierjean, C., Aubry, A., Wyckaert, F. & Boussard, G.</i>
Structural features of the Pip/AzPip couple in the crystalline state. Influence of the relative AzPip location in an azadipeptide sequence upon the induced chirality and conformational characteristics.</p>
<p>
<i>J. Peptide Res.</i>
, 2000,
<b>55,</b>
308–317.</p>
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<abstract>Abstract: Azapipecolic (AzPip) is a pipecolic (Pip) residue analogue containing a nitrogen atom in place of the CαH group. AzPip was introduced into two reverse dipeptide sequences,Piv‐AzPip‐l‐Ala‐NHiPr I and Boc‐l‐Ala‐AzPip‐NHiPr II in order to evaluate, in the crystalline state, the influence of thel‐Ala‐induced chirality upon the prochiral AzPip residue, and therefore the resulting conformational characteristics, according to the relative position of the AzPip residue. Piv‐dl‐Pip‐NHMe III served as a control derivative for comparison between the properties of the two different heterocycles of Pip and AzPip residues. Piperidine and hexahydropyridazine rings have a few characteristics in common: chair conformation, axial disposition of the C‐terminal backbone substituent and the cisoid form of the N‐terminal tertiary amide function. An almost pure sp3 hybridization state is observed for the substituted nitrogen atom Nα, so that l‐Ala induces an AzPip (R) or (S) chirality when it follows or precedes, respectively, the azaresidue in such a pseudodipeptide sequence. If both I and II compounds present a short NH…N contact between the sp2 tertiary amide nitrogen atom and the NH of the next secondary amide function, whatever the chiral nature of the sequence, the heterochiral azadipeptide I adopts a rather totally extended conformation while the homochiral azadipeptide II is folded by a β‐VI turn‐like structure stabilized by a classical 4→1 intramolecular hydrogen bond.</abstract>
<subject lang="en">
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<topic>azapeptide</topic>
<topic>azapeptide folding</topic>
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<topic>hexahydropyridazine‐N‐carboxylic acid</topic>
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