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Synthesis and crystal structures of new chiral 3-amino-2<i>H</i>-azirines and the Pd complex of one of them


Linden, Anthony; Bucher, Christoph B; Gubler, Ralf; Villalgordo, José M; Heimgartner, Heinz (2023). Synthesis and crystal structures of new chiral 3-amino-2<i>H</i>-azirines and the Pd complex of one of them. Acta Crystallographica. Section C: Structural Chemistry, 79(3):104-111.

Abstract

3-Amino-2H-azirines are potentially versatile building blocks in heterocyclic and peptide synthesis. Three new 3-amino-2H-azirines have been synthesized as racemates or mixtures of diastereoisomers in cases where another chiral residue is incorporated as the exocyclic amine. The crystal structures of two of them, an approximately 1:1 diastereoisomeric mixture of (2R)- and (2S)-2-ethyl-3-[(2S)-2-(1-methoxy-1,1-diphenylmethyl)pyrrolidin-1-yl]-2-methyl-2H-azirine, C23H28N2O, 11, and 2-benzyl-3-(N-methyl-N-phenylamino)-2-phenyl-2H-azirine, C22H20N2, 12, and the third as its diastereoisomeric trans-PdCl2 complex, trans-dichlorido[(2R)-2-ethyl-2-methyl-3-(X)-2H-azirine][(2S)-2-ethyl-2-methyl-3-(X)-2H-azirine]palladium(
II), where X = N-{[(1S,2S,5S)-6,6-dimethylbicyclo[3.1.1]heptan-2-yl]-methyl}-N-phenylamino, [PdCl2(C21H30N2)2], 14, have been determined and the geometries of the azirine rings compared with those of 11 other 3-amino-2Hazirine structures reported in the literature. Most notable is the very long formal N—C single bond, which is, with one exception, around 1.57 A ˚ . Each compound has crystallized in a chiral space group. The Pd atom in the trans-PdCl2 complex is coordinated by one of each of the pair of diastereoisomers, while both of the diastereoisomers share the same crystallographic site in the structure of 11; this property thereby manifesting itself as disorder. The chosen crystal of 12 is either an inversion twin or composed of a pure enantiomorph, but this could not be established specifically.

Abstract

3-Amino-2H-azirines are potentially versatile building blocks in heterocyclic and peptide synthesis. Three new 3-amino-2H-azirines have been synthesized as racemates or mixtures of diastereoisomers in cases where another chiral residue is incorporated as the exocyclic amine. The crystal structures of two of them, an approximately 1:1 diastereoisomeric mixture of (2R)- and (2S)-2-ethyl-3-[(2S)-2-(1-methoxy-1,1-diphenylmethyl)pyrrolidin-1-yl]-2-methyl-2H-azirine, C23H28N2O, 11, and 2-benzyl-3-(N-methyl-N-phenylamino)-2-phenyl-2H-azirine, C22H20N2, 12, and the third as its diastereoisomeric trans-PdCl2 complex, trans-dichlorido[(2R)-2-ethyl-2-methyl-3-(X)-2H-azirine][(2S)-2-ethyl-2-methyl-3-(X)-2H-azirine]palladium(
II), where X = N-{[(1S,2S,5S)-6,6-dimethylbicyclo[3.1.1]heptan-2-yl]-methyl}-N-phenylamino, [PdCl2(C21H30N2)2], 14, have been determined and the geometries of the azirine rings compared with those of 11 other 3-amino-2Hazirine structures reported in the literature. Most notable is the very long formal N—C single bond, which is, with one exception, around 1.57 A ˚ . Each compound has crystallized in a chiral space group. The Pd atom in the trans-PdCl2 complex is coordinated by one of each of the pair of diastereoisomers, while both of the diastereoisomers share the same crystallographic site in the structure of 11; this property thereby manifesting itself as disorder. The chosen crystal of 12 is either an inversion twin or composed of a pure enantiomorph, but this could not be established specifically.

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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
Uncontrolled Keywords:3-amino-2H-azirines; azirine rings; crystal structure; diastereoisomers; Pd–azirine complex; organic synthesis
Language:English
Date:1 March 2023
Deposited On:16 Mar 2023 09:01
Last Modified:30 Mar 2024 02:34
Publisher:Wiley-Blackwell Publishing, Inc.
ISSN:2053-2296
OA Status:Hybrid
Free access at:PubMed ID. An embargo period may apply.
Publisher DOI:https://doi.org/10.1107/s2053229623001468
PubMed ID:36871292
Project Information:
  • : FunderAlfred Werner Legat
  • : Grant ID
  • : Project Title
  • : FunderProf. Dr. Hans E. Schmid-Stiftung
  • : Grant ID
  • : Project Title
  • : FunderSwiss National Science Foundation
  • : Grant ID
  • : Project Title
  • : FunderF. Hoffmann-La Roche AG, Basel
  • : Grant ID
  • : Project Title
  • Content: Published Version
  • Language: English
  • Licence: Creative Commons: Attribution 4.0 International (CC BY 4.0)