Preparation and X-ray crystal study of benziodoxaborole derivatives

New hypervalent iodine heterocycles

Victor N. Nemykin, Andrey V. Maskaev, Margarita R. Geraskina, Mekhman S. Yusubov, Viktor Vladimirovich Zhdankin

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

A series of heterocyclic compounds containing trivalent iodine, oxygen, and boron in a five-membered ring were prepared and structurally investigated by X-ray crystallography. 1-Chloro-4-fluoro-1H-1λ 3-benzo[d][1,2, 3]iodoxoborol-3-ol was synthesized by chlorination of 2-fluoro-6- iodophenylboronic acid followed by treatment of the intermediate iododichloride with water. 1-Acetoxy-4-fluoro-1H-1λ 3-benzo[d][1,2,3] iodoxoborol-3-ol, 1-acetoxy-1H-1λ 3-benzo[d][1,2,3]iodoxoborol- 3-ol, and similar 1-substituted trifluoroacetate derivatives of benziodoxaborole were prepared the hypochlorite oxidation of 2-fluoro-6-iodophenylboronic acid or 2-iodophenylboronic acid in acetic or trifluoroacetic acid, respectively. 1-Acetoxy substituted benziodoxaborole can be further converted to the respective trifluoroacetate by treatment with trifluoroacetic acid or to the 1-hydroxy derivative by basic hydrolysis with aqueous NaHCO 3. X-ray structural studies of 1-chloro-and 1-trifluoroacetoxy substituted benziodoxaboroles 13, 17, and 18 have shown the presence of a planar five-membered heterocyclic ring with unusually short endocyclic I-O bond distance of 2.04-2.09 Å. Slow crystallization of 4-fluoro-1- trifluoroacetoxy-1H-1λ 3-benzo[d][1,2,3]iodoxoborol-3-ol from methanol resulted in the formation of a tetrameric macrocyclic structure 21 resulting from self-assembly of the initially formed 4-fluoro-1,3-dimethoxy-1H- 1λ 3-benzo[d][1,2,3]iodoxoborol. Structural parameters of the five-membered iodoxoborol ring, such as the planar geometry and the short B-O and O-I bonds lengths in 13, 17, and 18 compared to those in 21 and known benziodoxoles are indicative of partially aromatic character of this ring. Density functional theory (DFT) predicted NIST (0) and NIST (1) indexes for 1-chloro-and 1-trifluoroacetoxy substituted benziodoxaboroles, however, are indicative of significantly lower aromaticity compared to the classic aromatic systems.

Original languageEnglish
Pages (from-to)11263-11272
Number of pages10
JournalInorganic Chemistry
Volume50
Issue number21
DOIs
Publication statusPublished - 7 Nov 2011

Fingerprint

Trifluoroacetic Acid
Iodine
iodine
Derivatives
X rays
preparation
Crystals
acids
rings
Acids
crystals
x rays
Heterocyclic Compounds
Hypochlorous Acid
Boron
Chlorination
X ray crystallography
Bond length
heterocyclic compounds
Crystallization

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Preparation and X-ray crystal study of benziodoxaborole derivatives : New hypervalent iodine heterocycles. / Nemykin, Victor N.; Maskaev, Andrey V.; Geraskina, Margarita R.; Yusubov, Mekhman S.; Zhdankin, Viktor Vladimirovich.

In: Inorganic Chemistry, Vol. 50, No. 21, 07.11.2011, p. 11263-11272.

Research output: Contribution to journalArticle

@article{5a70db709895421591de244c0023e791,
title = "Preparation and X-ray crystal study of benziodoxaborole derivatives: New hypervalent iodine heterocycles",
abstract = "A series of heterocyclic compounds containing trivalent iodine, oxygen, and boron in a five-membered ring were prepared and structurally investigated by X-ray crystallography. 1-Chloro-4-fluoro-1H-1λ 3-benzo[d][1,2, 3]iodoxoborol-3-ol was synthesized by chlorination of 2-fluoro-6- iodophenylboronic acid followed by treatment of the intermediate iododichloride with water. 1-Acetoxy-4-fluoro-1H-1λ 3-benzo[d][1,2,3] iodoxoborol-3-ol, 1-acetoxy-1H-1λ 3-benzo[d][1,2,3]iodoxoborol- 3-ol, and similar 1-substituted trifluoroacetate derivatives of benziodoxaborole were prepared the hypochlorite oxidation of 2-fluoro-6-iodophenylboronic acid or 2-iodophenylboronic acid in acetic or trifluoroacetic acid, respectively. 1-Acetoxy substituted benziodoxaborole can be further converted to the respective trifluoroacetate by treatment with trifluoroacetic acid or to the 1-hydroxy derivative by basic hydrolysis with aqueous NaHCO 3. X-ray structural studies of 1-chloro-and 1-trifluoroacetoxy substituted benziodoxaboroles 13, 17, and 18 have shown the presence of a planar five-membered heterocyclic ring with unusually short endocyclic I-O bond distance of 2.04-2.09 {\AA}. Slow crystallization of 4-fluoro-1- trifluoroacetoxy-1H-1λ 3-benzo[d][1,2,3]iodoxoborol-3-ol from methanol resulted in the formation of a tetrameric macrocyclic structure 21 resulting from self-assembly of the initially formed 4-fluoro-1,3-dimethoxy-1H- 1λ 3-benzo[d][1,2,3]iodoxoborol. Structural parameters of the five-membered iodoxoborol ring, such as the planar geometry and the short B-O and O-I bonds lengths in 13, 17, and 18 compared to those in 21 and known benziodoxoles are indicative of partially aromatic character of this ring. Density functional theory (DFT) predicted NIST (0) and NIST (1) indexes for 1-chloro-and 1-trifluoroacetoxy substituted benziodoxaboroles, however, are indicative of significantly lower aromaticity compared to the classic aromatic systems.",
author = "Nemykin, {Victor N.} and Maskaev, {Andrey V.} and Geraskina, {Margarita R.} and Yusubov, {Mekhman S.} and Zhdankin, {Viktor Vladimirovich}",
year = "2011",
month = "11",
day = "7",
doi = "10.1021/ic201922n",
language = "English",
volume = "50",
pages = "11263--11272",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Preparation and X-ray crystal study of benziodoxaborole derivatives

T2 - New hypervalent iodine heterocycles

AU - Nemykin, Victor N.

AU - Maskaev, Andrey V.

AU - Geraskina, Margarita R.

AU - Yusubov, Mekhman S.

AU - Zhdankin, Viktor Vladimirovich

PY - 2011/11/7

Y1 - 2011/11/7

N2 - A series of heterocyclic compounds containing trivalent iodine, oxygen, and boron in a five-membered ring were prepared and structurally investigated by X-ray crystallography. 1-Chloro-4-fluoro-1H-1λ 3-benzo[d][1,2, 3]iodoxoborol-3-ol was synthesized by chlorination of 2-fluoro-6- iodophenylboronic acid followed by treatment of the intermediate iododichloride with water. 1-Acetoxy-4-fluoro-1H-1λ 3-benzo[d][1,2,3] iodoxoborol-3-ol, 1-acetoxy-1H-1λ 3-benzo[d][1,2,3]iodoxoborol- 3-ol, and similar 1-substituted trifluoroacetate derivatives of benziodoxaborole were prepared the hypochlorite oxidation of 2-fluoro-6-iodophenylboronic acid or 2-iodophenylboronic acid in acetic or trifluoroacetic acid, respectively. 1-Acetoxy substituted benziodoxaborole can be further converted to the respective trifluoroacetate by treatment with trifluoroacetic acid or to the 1-hydroxy derivative by basic hydrolysis with aqueous NaHCO 3. X-ray structural studies of 1-chloro-and 1-trifluoroacetoxy substituted benziodoxaboroles 13, 17, and 18 have shown the presence of a planar five-membered heterocyclic ring with unusually short endocyclic I-O bond distance of 2.04-2.09 Å. Slow crystallization of 4-fluoro-1- trifluoroacetoxy-1H-1λ 3-benzo[d][1,2,3]iodoxoborol-3-ol from methanol resulted in the formation of a tetrameric macrocyclic structure 21 resulting from self-assembly of the initially formed 4-fluoro-1,3-dimethoxy-1H- 1λ 3-benzo[d][1,2,3]iodoxoborol. Structural parameters of the five-membered iodoxoborol ring, such as the planar geometry and the short B-O and O-I bonds lengths in 13, 17, and 18 compared to those in 21 and known benziodoxoles are indicative of partially aromatic character of this ring. Density functional theory (DFT) predicted NIST (0) and NIST (1) indexes for 1-chloro-and 1-trifluoroacetoxy substituted benziodoxaboroles, however, are indicative of significantly lower aromaticity compared to the classic aromatic systems.

AB - A series of heterocyclic compounds containing trivalent iodine, oxygen, and boron in a five-membered ring were prepared and structurally investigated by X-ray crystallography. 1-Chloro-4-fluoro-1H-1λ 3-benzo[d][1,2, 3]iodoxoborol-3-ol was synthesized by chlorination of 2-fluoro-6- iodophenylboronic acid followed by treatment of the intermediate iododichloride with water. 1-Acetoxy-4-fluoro-1H-1λ 3-benzo[d][1,2,3] iodoxoborol-3-ol, 1-acetoxy-1H-1λ 3-benzo[d][1,2,3]iodoxoborol- 3-ol, and similar 1-substituted trifluoroacetate derivatives of benziodoxaborole were prepared the hypochlorite oxidation of 2-fluoro-6-iodophenylboronic acid or 2-iodophenylboronic acid in acetic or trifluoroacetic acid, respectively. 1-Acetoxy substituted benziodoxaborole can be further converted to the respective trifluoroacetate by treatment with trifluoroacetic acid or to the 1-hydroxy derivative by basic hydrolysis with aqueous NaHCO 3. X-ray structural studies of 1-chloro-and 1-trifluoroacetoxy substituted benziodoxaboroles 13, 17, and 18 have shown the presence of a planar five-membered heterocyclic ring with unusually short endocyclic I-O bond distance of 2.04-2.09 Å. Slow crystallization of 4-fluoro-1- trifluoroacetoxy-1H-1λ 3-benzo[d][1,2,3]iodoxoborol-3-ol from methanol resulted in the formation of a tetrameric macrocyclic structure 21 resulting from self-assembly of the initially formed 4-fluoro-1,3-dimethoxy-1H- 1λ 3-benzo[d][1,2,3]iodoxoborol. Structural parameters of the five-membered iodoxoborol ring, such as the planar geometry and the short B-O and O-I bonds lengths in 13, 17, and 18 compared to those in 21 and known benziodoxoles are indicative of partially aromatic character of this ring. Density functional theory (DFT) predicted NIST (0) and NIST (1) indexes for 1-chloro-and 1-trifluoroacetoxy substituted benziodoxaboroles, however, are indicative of significantly lower aromaticity compared to the classic aromatic systems.

UR - http://www.scopus.com/inward/record.url?scp=80155142368&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=80155142368&partnerID=8YFLogxK

U2 - 10.1021/ic201922n

DO - 10.1021/ic201922n

M3 - Article

VL - 50

SP - 11263

EP - 11272

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 21

ER -