Oxidative fluorination with Selectfluor: A convenient procedure for preparing hypervalent iodine(V) fluorides.
Samuel M G Dearman1, Xiang Li2, Yang Li2
1School of Chemistry, University of Leicester, Leicester, LE1 7RH, UK.
Beilstein Journal of Organic Chemistry
|August 7, 2024
Summary
Researchers developed a mild method for synthesizing hypervalent iodine(V) fluorides using Selectfluor. This new approach offers improved yields and stability for these challenging compounds.
Area of Science:
- Organic Chemistry
- Fluorine Chemistry
- Hypervalent Iodine Compounds
Background:
- Hypervalent iodine(V) fluorides are valuable synthetic intermediates.
- Traditional synthesis methods employ harsh reagents, limiting accessibility and investigation.
- Developing milder and efficient synthetic routes is crucial for advancing fluorine chemistry.
Purpose of the Study:
- To establish a mild and efficient method for preparing hypervalent iodine(V) fluorides.
- To investigate the stability of novel hypervalent iodine(V) fluoride derivatives.
- To explore the factors influencing the stability of these compounds.
Main Methods:
- Utilized Selectfluor as a mild fluorinating agent for iodine(V) precursors.
- Synthesized bicyclic difluoro(aryl)-λ⁵-iodane derivatives.
- Conducted stability studies in different deuterated solvents (acetonitrile-d3 and chloroform-d1).
Main Results:
- Achieved good isolated yields (72-90%) for hypervalent iodine(V) fluorides using Selectfluor.
- Demonstrated enhanced stability of bicyclic difluoro(aryl)-λ⁵-iodane 6 in acetonitrile-d3 compared to chloroform-d1.
- Identified solvent coordination and halogen bonding as potential stabilization mechanisms.
Conclusions:
- Selectfluor provides a mild and effective reagent for synthesizing hypervalent iodine(V) fluorides.
- The stability of hypervalent iodine(V) fluorides is solvent-dependent.
- Acetonitrile's coordinating ability likely enhances the stability of iodine(V) species through halogen bonding.
More Related Videos
10:10Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
Published on: July 28, 2018
6.4K
08:43Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
10.2K
Related Concept Videos
01:13Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
5.9K
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
5.9K
02:33Preparation and Reactions of Thiols
6.1K
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
6.1K
03:01Halogens
18.4K
Group 17 elements, known as halogens, are nonmetals. At room temperature, fluorine and chlorine are gases, bromine is a liquid, and iodine a solid. Astatine is a highly unstable radioactive element, so currently, most of its properties are unknown due to its short half-life. Tennessine is a synthetic element also predicted to be in this group.
18.4K
01:23Redox Titration: Iodimetry and Iodometry
1.4K
Iodometry and iodimetry are analytical methods used to determine the concentration of oxidizing or reducing agents using iodine. In iodometric titrations, the oxidizing analyte solution is usually acidified and treated with an excess of iodide ions, which generates an equivalent amount of iodine in equilibrium with triiodide. The released iodine is subsequently titrated directly against a standardized reducing agent. As the dilute iodine color becomes pale yellow, a few drops of freshly...
1.4K
03:11Precipitation of Ions
27.8K
Predicting Precipitation
The equation that describes the equilibrium between solid calcium carbonate and its solvated ions is:
The equation that describes the equilibrium between solid calcium carbonate and its solvated ions is:
27.8K
00:51Base-Promoted α-Halogenation of Aldehydes and Ketones
3.4K
α-Halogenation of aldehydes and ketones is a reaction involving the substitution of α hydrogens with halogens in the presence of a base. The reaction begins with the abstraction of α hydrogen by the base to produce a nucleophilic enolate ion. This intermediate undergoes a subsequent nucleophilic substitution with the halogen to produce a monohalogenated carbonyl compound. If the starting substrate has more than one α hydrogen, it is difficult to stop the reaction...
3.4K