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Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene

Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene

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.

Electrophilic Aromatic Substitution: Friedel–Crafts Acylation of Benzene

Electrophilic Aromatic Substitution: Friedel–Crafts Acylation of Benzene

The Friedel–Crafts acylation reactions involve the addition of an acyl group to an aromatic ring. These reactions proceed via electrophilic aromatic substitution by employing an acyl chloride and a Lewis acid catalyst such as aluminum chloride to form aryl ketone.

Thermal and Photochemical Electrocyclic Reactions: Overview

Thermal and Photochemical Electrocyclic Reactions: Overview

Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.

Thermal Electrocyclic Reactions: Stereochemistry

Thermal Electrocyclic Reactions: Stereochemistry

The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

Electrophilic Aromatic Substitution: Friedel–Crafts Alkylation of Benzene

Electrophilic Aromatic Substitution: Friedel–Crafts Alkylation of Benzene

Friedel–Crafts reactions were developed in 1877 by the French chemist Charles Friedel and the American chemist James Crafts. Friedel–Crafts alkylation refers to the replacement of an aromatic proton with an alkyl group via electrophilic aromatic substitution. A Lewis acid catalyst such as aluminum chloride reacts with an alkyl halide to form a carbocation. The resulting carbocation then reacts with the aromatic ring and undergoes a series of electron rearrangements before giving the...

Photochemical Electrocyclic Reactions: Stereochemistry

Photochemical Electrocyclic Reactions: Stereochemistry

The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation

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Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

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Electrooxidative Fluorofunctionalization of Arylcyclopropanes.

Yanni Yue^1,2, Yang Song¹, Shuaishuai Zhao¹

¹Technical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis (IAS), State Key Laboratory of Material-Oriented Chemical Engineering, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China.

Organic Letters

|September 28, 2023

Summary

This study presents a novel electrochemical method for fluorinating arylcyclopropanes without catalysts or oxidants. The process efficiently achieves 1,3-fluorofunctionalization and subsequent reactions with various nucleophiles.

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Area of Science:

Organic Chemistry
Electrochemistry
Fluorination Chemistry

Background:

1,3-Fluorofunctionalization of cyclopropanes is synthetically challenging.
Existing methods often require harsh conditions, catalysts, or stoichiometric oxidants.

Purpose of the Study:

To develop a novel, efficient, and sustainable method for 1,3-fluorofunctionalization of arylcyclopropanes.
To achieve catalyst- and oxidant-free conditions using electrochemistry.

Main Methods:

Electrochemical oxidation of arylcyclopropanes.
Utilizing tetrafluoroborate (BF4-) as the fluoride source and counterion.
Integration of various nucleophiles (alcohols, acids, N-heterocycles) for subsequent functionalization.

Main Results:

Demonstrated the viability of an electrochemical oxidative protocol for 1,3-fluorofunctionalization.
Achieved catalyst- and oxidant-free conditions.
Successfully synthesized 1,3-fluorooxygenation and 1,3-fluoroamination products.

Conclusions:

The developed electrochemical method offers an expedient route to valuable fluorinated organic compounds.
The mechanism involves nucleophilic attack initiated by a tight ion pair between the aryl radical cation and the BF4- counterion.
This approach provides a versatile platform for synthesizing diverse fluorinated molecules.