Electrophilic Aromatic Substitution of Groups other than Hydrogen. Part I:Ipso Factors and Rate-Limiting Steps in Dehalogenations by Diazonium Ions. 26th communication on diazo coupling reactions

1972 ◽  
Vol 55 (6) ◽  
pp. 2139-2146 ◽  
Author(s):  
P. B. Fischer ◽  
H. Zollinger
Keyword(s):  
Electrophilic Aromatic Substitution ◽  
Coupling Reactions ◽  
Aromatic Substitution ◽  
Diazo Coupling ◽  
Diazonium Ions ◽  
Rate Limiting

scholarly journals Site-selective covalent functionalization at interior carbon atoms and on the rim of circumtrindene, a C36H12 open geodesic polyarene

2014 ◽  
Vol 10 ◽  
pp. 956-968 ◽  
Author(s):  
Hee Yeon Cho ◽  
Ronald B M Ansems ◽  
Lawrence T Scott
Keyword(s):  
Aromatic Hydrocarbons ◽  
Electrophilic Aromatic Substitution ◽  
Coupling Reactions ◽  
Computational Results ◽  
Aromatic Substitution ◽  
Covalent Functionalization ◽  
Polycyclic Aromatic ◽  
Site Selective ◽  
Geodesic Polyarenes ◽  
Derivatives Of

Circumtrindene (6, C36H12), one of the largest open geodesic polyarenes ever reported, exhibits fullerene-like reactivity at its interior carbon atoms, whereas its edge carbons react like those of planar polycyclic aromatic hydrocarbons (PAHs). The Bingel–Hirsch and Prato reactions – two traditional methods for fullerene functionalization – afford derivatives of circumtrindene with one of the interior 6:6 C=C bonds modified. On the other hand, functionalization on the rim of circumtrindene can be achieved by normal electrophilic aromatic substitution, the most common reaction of planar PAHs. This peripheral functionalization has been used to extend the π-system of the polyarene by subsequent coupling reactions and to probe the magnetic environment of the concave/convex space around the hydrocarbon bowl. For both classes of functionalization, computational results are reported to complement the experimental observations.

Synthesis of Aromatic and Aliphatic Di-, Tri-, and Tetrasulfonic Acids

Synlett ◽  
2020 ◽  
Vol 31 (10) ◽  
pp. 945-952
Author(s):  
Jens Christoffers ◽  
Mathias S. Wickleder
Keyword(s):  
Nucleophilic Aromatic Substitution ◽  
Electrophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Nucleophilic Substitutions ◽  
Sulfonic Acids ◽  
Subsequent Oxidation ◽  
Aromatic Substrates ◽  
Diazonium Ions ◽  
Metal Organic

Oligosulfonic acids are promising linker compounds for coordination polymers and metal-organic frameworks, however, compared to their carboxylic acid congeners, often not readily accessible by established synthetic routes. This Account highlights the synthesis of recently developed aromatic and aliphatic di-, tri- and tetrasulfonic acids. While multiple electrophilic sulfonations of aromatic substrates are rather limited, the nucleophilic aromatic substitution including an intramolecular variant, the Newman–Kwart rearrangement, allows the flexible introduction of up to four sulfur-containing moieties at an aromatic ring. Sulfonic acids are then accessed by oxidation of thiols, thioethers, or thioesters either directly with hydrogen peroxide or in two steps with chlorine (generated in situ from N-chlorosuccinimide/hydrochloric acid) to furnish sulfochlorides which are subsequently hydrolyzed. In the aliphatic series, secondary alcohols as starting materials are converted into thioethers, thioesters, or thiocarbonates by nucleophilic substitutions, which are also subsequently oxidized to furnish sulfonic acids.1 Introduction2 Electrophilic Aromatic Substitution3 Nucleophilic Aromatic Substitution3.1 Intermolecular SNAr3.2 Intermolecular with Subsequent Oxidation3.3 Intramolecular with Subsequent Oxidation4 Nucleophilic Aliphatic Substitution with Subsequent Oxidation5 Oxidation5.1 Oxidation of Thiocarbonates5.2 Oxidation of Thioethers5.3 Oxidation of Thioesters6 Thermolysis of Neopentylsulfonates7 Functionalization via Diazonium Ions8 Conclusion

scholarly journals Desulfination by 2′-hydroxybiphenyl-2-sulfinate desulfinase proceeds via electrophilic aromatic substitution by the cysteine-27 proton

2017 ◽  
Vol 8 (7) ◽  
pp. 5078-5086 ◽  
Author(s):  
Inacrist Geronimo ◽  
Shawn R. Nigam ◽  
Christina M. Payne
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Electrophilic Substitution ◽  
Electrophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Functional Theory ◽  
Rate Limiting

Density functional theory shows that the rate-limiting desulfination step in biodesulfurization involves concerted electrophilic substitution with the Cys-27 proton.

Sign in / Sign up

Export Citation Format

Share Document