Reactions of 1-Arylbenziodoxolones with Azide Anion

Experimental and Computational Study of Substituent Effects

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

New substituted 1-arylbenziodoxolones were prepared and their reactivity with azide anion as a nucleophile was investigated. It was found that independent of the presence of substituents, all reactions of 1-arylbenziodoxolones proceed as nucleophilic substitution of the iodonium leaving group in the electron-deficient benziodoxolone benzene ring. The presence of bulky substituents in the ortho position of the aryl ring slows the reaction down, while the presence of a moderately electron-withdrawing bromine substituent in para position to the iodine atom in the benziodoxolone ring moderately increases the rate of substitution. The presence of a strongly electron-withdrawing nitro group in the para position to the iodine atom in the benziodoxolone ring dramatically increases the rate of substitution. These observations are in agreement with the electronic requirements for internal nucleophilic substitution in the benziodoxole ring. A quantum-chemical computational study of the possible reaction paths is in agreement with the observed effects of substituents on the reactivity of arylbenziodoxolones in this reaction.

Original languageEnglish
Pages (from-to)640-647
Number of pages8
JournalEuropean Journal of Organic Chemistry
Volume2018
Issue number5
DOIs
Publication statusPublished - 7 Feb 2018

Fingerprint

Azides
Anions
Substitution reactions
anions
rings
substitutes
Iodine
Electrons
iodine
Bromine
Atoms
reactivity
Nucleophiles
Benzene
electrons
nucleophiles
bromine
atoms
benzene
requirements

Keywords

  • Density functional calculations
  • Hypervalent Iodine
  • Iodine
  • Synthetic methods

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

@article{a3f4caf113574686a931aec98ad8e7e9,
title = "Reactions of 1-Arylbenziodoxolones with Azide Anion: Experimental and Computational Study of Substituent Effects",
abstract = "New substituted 1-arylbenziodoxolones were prepared and their reactivity with azide anion as a nucleophile was investigated. It was found that independent of the presence of substituents, all reactions of 1-arylbenziodoxolones proceed as nucleophilic substitution of the iodonium leaving group in the electron-deficient benziodoxolone benzene ring. The presence of bulky substituents in the ortho position of the aryl ring slows the reaction down, while the presence of a moderately electron-withdrawing bromine substituent in para position to the iodine atom in the benziodoxolone ring moderately increases the rate of substitution. The presence of a strongly electron-withdrawing nitro group in the para position to the iodine atom in the benziodoxolone ring dramatically increases the rate of substitution. These observations are in agreement with the electronic requirements for internal nucleophilic substitution in the benziodoxole ring. A quantum-chemical computational study of the possible reaction paths is in agreement with the observed effects of substituents on the reactivity of arylbenziodoxolones in this reaction.",
keywords = "Density functional calculations, Hypervalent Iodine, Iodine, Synthetic methods",
author = "Yusubov, {Mekhman S.} and Soldatova, {Natalia S.} and Postnikov, {Pavel S.} and Valiev, {Rashid R.} and Svitich, {Dmitry Y.} and Yusubova, {Roza Y.} and Akira Yoshimura and Thomas Wirth and Zhdankin, {Viktor V.}",
year = "2018",
month = "2",
day = "7",
doi = "10.1002/ejoc.201701595",
language = "English",
volume = "2018",
pages = "640--647",
journal = "Annalen der Pharmacie",
issn = "0075-4617",
publisher = "Wiley-VCH Verlag",
number = "5",

}

TY - JOUR

T1 - Reactions of 1-Arylbenziodoxolones with Azide Anion

T2 - Experimental and Computational Study of Substituent Effects

AU - Yusubov, Mekhman S.

AU - Soldatova, Natalia S.

AU - Postnikov, Pavel S.

AU - Valiev, Rashid R.

AU - Svitich, Dmitry Y.

AU - Yusubova, Roza Y.

AU - Yoshimura, Akira

AU - Wirth, Thomas

AU - Zhdankin, Viktor V.

PY - 2018/2/7

Y1 - 2018/2/7

N2 - New substituted 1-arylbenziodoxolones were prepared and their reactivity with azide anion as a nucleophile was investigated. It was found that independent of the presence of substituents, all reactions of 1-arylbenziodoxolones proceed as nucleophilic substitution of the iodonium leaving group in the electron-deficient benziodoxolone benzene ring. The presence of bulky substituents in the ortho position of the aryl ring slows the reaction down, while the presence of a moderately electron-withdrawing bromine substituent in para position to the iodine atom in the benziodoxolone ring moderately increases the rate of substitution. The presence of a strongly electron-withdrawing nitro group in the para position to the iodine atom in the benziodoxolone ring dramatically increases the rate of substitution. These observations are in agreement with the electronic requirements for internal nucleophilic substitution in the benziodoxole ring. A quantum-chemical computational study of the possible reaction paths is in agreement with the observed effects of substituents on the reactivity of arylbenziodoxolones in this reaction.

AB - New substituted 1-arylbenziodoxolones were prepared and their reactivity with azide anion as a nucleophile was investigated. It was found that independent of the presence of substituents, all reactions of 1-arylbenziodoxolones proceed as nucleophilic substitution of the iodonium leaving group in the electron-deficient benziodoxolone benzene ring. The presence of bulky substituents in the ortho position of the aryl ring slows the reaction down, while the presence of a moderately electron-withdrawing bromine substituent in para position to the iodine atom in the benziodoxolone ring moderately increases the rate of substitution. The presence of a strongly electron-withdrawing nitro group in the para position to the iodine atom in the benziodoxolone ring dramatically increases the rate of substitution. These observations are in agreement with the electronic requirements for internal nucleophilic substitution in the benziodoxole ring. A quantum-chemical computational study of the possible reaction paths is in agreement with the observed effects of substituents on the reactivity of arylbenziodoxolones in this reaction.

KW - Density functional calculations

KW - Hypervalent Iodine

KW - Iodine

KW - Synthetic methods

UR - http://www.scopus.com/inward/record.url?scp=85041406777&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85041406777&partnerID=8YFLogxK

U2 - 10.1002/ejoc.201701595

DO - 10.1002/ejoc.201701595

M3 - Article

VL - 2018

SP - 640

EP - 647

JO - Annalen der Pharmacie

JF - Annalen der Pharmacie

SN - 0075-4617

IS - 5

ER -