10-Membered Azaenediyne Fused to a Benzothiophene through the Nicholas Macrocyclization: Synthesis and DNA Cleavage Ability

Natalia A. Danilkina, Andrey M. Rumyantsev, Anna L. Lyapunova, Alexander S. D'Yachenko, Alexander F. Khlebnikov, Irina A. Balova

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The Nicholas-type macrocyclization through NH-tosyl functional group has been found to be an efficient technique for the synthesis of a 10-membered azaenediyne system annulated with a benzothiophene. To compare the activity of azaenediyne synthesized with similar oxa- and carbocyclic enediynes the Bergman cyclization activation energies and the ability of enediynes to cleave DNA (pBR322 plasmid) were investigated. The order of reactivity predicted by DFT calculations (N -enediyne < C -enediyne < O -enediyne) was confirmed by DSC analysis data. Surprisingly azaenediyne was found to be more active in the DNA cleavage assay than the C-analogue.

LanguageEnglish
Article numberst-2018-b0536-l
Pages161-166
Number of pages6
JournalSynlett
Volume30
Issue number2
DOIs
StatePublished - 1 Jan 2019

Keywords

  • alkyne
  • benzothiophene
  • Bergman cyclization
  • enediyne
  • iodocyclization
  • Nicholas reaction
  • pBR322 plasmid

Scopus subject areas

  • Organic Chemistry

Cite this

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title = "10-Membered Azaenediyne Fused to a Benzothiophene through the Nicholas Macrocyclization: Synthesis and DNA Cleavage Ability",
abstract = "The Nicholas-type macrocyclization through NH-tosyl functional group has been found to be an efficient technique for the synthesis of a 10-membered azaenediyne system annulated with a benzothiophene. To compare the activity of azaenediyne synthesized with similar oxa- and carbocyclic enediynes the Bergman cyclization activation energies and the ability of enediynes to cleave DNA (pBR322 plasmid) were investigated. The order of reactivity predicted by DFT calculations (N -enediyne < C -enediyne < O -enediyne) was confirmed by DSC analysis data. Surprisingly azaenediyne was found to be more active in the DNA cleavage assay than the C-analogue.",
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10-Membered Azaenediyne Fused to a Benzothiophene through the Nicholas Macrocyclization : Synthesis and DNA Cleavage Ability. / Danilkina, Natalia A.; Rumyantsev, Andrey M.; Lyapunova, Anna L.; D'Yachenko, Alexander S.; Khlebnikov, Alexander F.; Balova, Irina A.

In: Synlett, Vol. 30, No. 2, st-2018-b0536-l, 01.01.2019, p. 161-166.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - 10-Membered Azaenediyne Fused to a Benzothiophene through the Nicholas Macrocyclization

T2 - Synlett

AU - Danilkina, Natalia A.

AU - Rumyantsev, Andrey M.

AU - Lyapunova, Anna L.

AU - D'Yachenko, Alexander S.

AU - Khlebnikov, Alexander F.

AU - Balova, Irina A.

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KW - benzothiophene

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KW - enediyne

KW - iodocyclization

KW - Nicholas reaction

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