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Synthesis of Seven Indolizine-Derived Pentathiepines: Strong Electronic Structure Response to Nitro Substitution in Position C-9.
Tallarita, Roberto; Jacobsen, Lukas Manuel; Elvers, Benedict J; Richter, Stefan; Bandaru, Siva S M; Correia, Jevy V; Schulzke, Carola.
Afiliação
  • Tallarita R; Bioinorganic Chemistry, Institute of Biochemistry, University of Greifswald, Felix-Hausdorff-Str. 4, 17489 Greifswald, Germany.
  • Jacobsen LM; Bioinorganic Chemistry, Institute of Biochemistry, University of Greifswald, Felix-Hausdorff-Str. 4, 17489 Greifswald, Germany.
  • Elvers BJ; Bioinorganic Chemistry, Institute of Biochemistry, University of Greifswald, Felix-Hausdorff-Str. 4, 17489 Greifswald, Germany.
  • Richter S; Bioinorganic Chemistry, Institute of Biochemistry, University of Greifswald, Felix-Hausdorff-Str. 4, 17489 Greifswald, Germany.
  • Bandaru SSM; Bioinorganic Chemistry, Institute of Biochemistry, University of Greifswald, Felix-Hausdorff-Str. 4, 17489 Greifswald, Germany.
  • Correia JV; Bioinorganic Chemistry, Institute of Biochemistry, University of Greifswald, Felix-Hausdorff-Str. 4, 17489 Greifswald, Germany.
  • Schulzke C; Bioinorganic Chemistry, Institute of Biochemistry, University of Greifswald, Felix-Hausdorff-Str. 4, 17489 Greifswald, Germany.
Molecules ; 29(1)2023 Dec 30.
Article em En | MEDLINE | ID: mdl-38202800
ABSTRACT
Seven new 1,2,3,4,5-pentathiepino[6,7-a]indolizines were synthesized in which the pentathiepine moieties bear an indolizine backbone that is derivatized from C-H to F-, Cl-, Br-, I-, NO2-, and CH3-substitutions, respectively, in a meta position relative to the aza group on the pyridine moiety. Their preparation took place via two common

steps:

(i) a Sonogashira coupling between (4-substituted) 2-bromo- or 2-chloropyridines and propynyl 3,3-diethylacetal, and (ii) a ring closing reaction mediated by a molybdenum oxo-bistetrasulfido complex and elemental sulfur. The latter simultaneously facilitates the 1,2,3,4,5-pentathiepino chain/ring- and indolizine ring-formations. The fluoro derivative was addressed with 2-bromo-5-aminopyridine as the starting material via a Sandmeyer reaction. The iodo derivative was obtained from 5-bromo-2-alkynylpiridine using a metal-assisted variation of the Finkelstein reaction. The requirement to explore different reaction conditions and the varied respective yields of the final products are discussed. The influence of the distinct substitutions on the pyridine moieties, their electronic structures, and respective chemical properties was investigated through a set of spectroscopic/analytical characterizations. Intriguingly, in all cases, the nitro-substituted derivative exhibited a distinct behavior compared to the six other investigated derivatives, which was also addressed computationally. All seven new pentathiepines were crystallized, and their respective molecular structures were determined using single crystal X-ray diffraction. These structures are compared and discussed as are their respective packing patterns.
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Revista: Molecules Assunto da revista: BIOLOGIA Ano de publicação: 2023 Tipo de documento: Article País de afiliação: Alemanha

Texto completo: 1 Base de dados: MEDLINE Idioma: En Revista: Molecules Assunto da revista: BIOLOGIA Ano de publicação: 2023 Tipo de documento: Article País de afiliação: Alemanha