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Solid-state conformations of linear depsipeptide amides with an alternating sequence of α,α-disubstituted α-amino acid and α-hy­droxy acid


Linden, Anthony; Magirius, J E Florian; Heimgartner, Heinz (2020). Solid-state conformations of linear depsipeptide amides with an alternating sequence of α,α-disubstituted α-amino acid and α-hy­droxy acid. Acta Crystallographica. Section C: Structural Chemistry, C76:1-9.

Abstract

Depsipeptides and cyclodepsipeptides are analogues of the corresponding peptides in which one or more amide groups are replaced by ester functions. Reports of crystal structures of linear depsipeptides are rare. The crystal structures and conformational analyses of four depsipeptides with an alternating sequence of an α,α-disubstituted α-amino acid and an α-hy­droxy acid are reported. The mol­ecules in the linear hexa­depsipeptide amide in (S)-Pms-Acp-(S)-Pms-Acp-(S)-Pms-Acp-NMe2 aceto­nitrile solvate, C47H58N4O9·C2H3N, (3b), as well as in the related linear tetra­depsipeptide amide (S)-Pms-Aib-(S)-Pms-Aib-NMe2, C28H37N3O6, (5a), the diastereoisomeric mixture (S,R)-Pms-Acp-(R,S)-Pms-Acp-NMe2/(R,S)-Pms-Acp-(R,S)-Pms-Acp-NMe2 (1:1), C32H41N3O6, (5b), and (R,S)-Mns-Acp-(S,R)-Mns-Acp-NMe2, C30H37N3O6, (5c) (Pms is phenyl­lactic acid, Acp is 1-amino­cyclo­pentane­carb­oxy­lic acid and Mns is mandelic acid), generally adopt a β-turn conformation in the solid state, which is stabilized by intra­molecular N—H...O hydrogen bonds. Whereas β-turns of type I (or I′) are formed in the cases of (3b), (5a) and (5b), which contain phenyl­lactic acid, the torsion angles for (5c), which incorporates mandelic acid, indicate a β-turn in between type I and type III. Inter­molecular N—H...O and O—H...O hydrogen bonds link the mol­ecules of (3a) and (5b) into extended chains, and those of (5a) and (5c) into two-dimensional networks.

Abstract

Depsipeptides and cyclodepsipeptides are analogues of the corresponding peptides in which one or more amide groups are replaced by ester functions. Reports of crystal structures of linear depsipeptides are rare. The crystal structures and conformational analyses of four depsipeptides with an alternating sequence of an α,α-disubstituted α-amino acid and an α-hy­droxy acid are reported. The mol­ecules in the linear hexa­depsipeptide amide in (S)-Pms-Acp-(S)-Pms-Acp-(S)-Pms-Acp-NMe2 aceto­nitrile solvate, C47H58N4O9·C2H3N, (3b), as well as in the related linear tetra­depsipeptide amide (S)-Pms-Aib-(S)-Pms-Aib-NMe2, C28H37N3O6, (5a), the diastereoisomeric mixture (S,R)-Pms-Acp-(R,S)-Pms-Acp-NMe2/(R,S)-Pms-Acp-(R,S)-Pms-Acp-NMe2 (1:1), C32H41N3O6, (5b), and (R,S)-Mns-Acp-(S,R)-Mns-Acp-NMe2, C30H37N3O6, (5c) (Pms is phenyl­lactic acid, Acp is 1-amino­cyclo­pentane­carb­oxy­lic acid and Mns is mandelic acid), generally adopt a β-turn conformation in the solid state, which is stabilized by intra­molecular N—H...O hydrogen bonds. Whereas β-turns of type I (or I′) are formed in the cases of (3b), (5a) and (5b), which contain phenyl­lactic acid, the torsion angles for (5c), which incorporates mandelic acid, indicate a β-turn in between type I and type III. Inter­molecular N—H...O and O—H...O hydrogen bonds link the mol­ecules of (3a) and (5b) into extended chains, and those of (5a) and (5c) into two-dimensional networks.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Condensed Matter Physics
Physical Sciences > Physical and Theoretical Chemistry
Physical Sciences > Inorganic Chemistry
Physical Sciences > Materials Chemistry
Language:English
Date:9 December 2020
Deposited On:09 Jan 2020 09:30
Last Modified:29 Jul 2020 12:14
Publisher:Wiley-Blackwell Publishing, Inc.
ISSN:2053-2296
OA Status:Hybrid
Publisher DOI:https://doi.org/10.1107/S2053229619016073
Project Information:
  • : FunderStipendienfonds der Basler Chemischen Industrie
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  • : Project Title
  • : FunderSwiss National Science Foundation
  • : Grant ID
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  • : FunderF. Hoffmann-La Roche AG, Basel
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