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

Research output

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.

Original languageEnglish
Pages (from-to)161-166
JournalSynlett
Volume30
Issue number2
DOIs
Publication statusPublished - 1 Jan 2019

Fingerprint

Enediynes
DNA
Cyclization
Discrete Fourier transforms
Functional groups
Assays
Plasmids
Activation energy
benzothiophene

Scopus subject areas

  • Organic Chemistry

Cite this

@article{e90f52dcf3524d8a85ab04329652e814,
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.",
keywords = "alkyne, benzothiophene, Bergman cyclization, enediyne, iodocyclization, Nicholas reaction, pBR322 plasmid",
author = "Danilkina, {Natalia A.} and Rumyantsev, {Andrey M.} and Lyapunova, {Anna L.} and D'Yachenko, {Alexander S.} and Khlebnikov, {Alexander F.} and Balova, {Irina A.}",
year = "2019",
month = "1",
day = "1",
doi = "10.1055/s-0037-1610352",
language = "English",
volume = "30",
pages = "161--166",
journal = "Synlett",
issn = "0936-5214",
publisher = "Georg Thieme Verlag",
number = "2",

}

TY - JOUR

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

T2 - Synthesis and DNA Cleavage Ability

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.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - 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.

AB - 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.

KW - alkyne

KW - benzothiophene

KW - Bergman cyclization

KW - enediyne

KW - iodocyclization

KW - Nicholas reaction

KW - pBR322 plasmid

UR - http://www.scopus.com/inward/record.url?scp=85059752476&partnerID=8YFLogxK

U2 - 10.1055/s-0037-1610352

DO - 10.1055/s-0037-1610352

M3 - Article

AN - SCOPUS:85059752476

VL - 30

SP - 161

EP - 166

JO - Synlett

JF - Synlett

SN - 0936-5214

IS - 2

ER -