Pyridine promotes dediazoniation of aryldiazonium tetrafluoroborates. The formed aryl radicals were trapped with B2pin2, iodine, or tetrahydrofuran to afford boronic esters, iodobenzenes and benzenes, respectively. The application to the synthesis of (pentafluorosulfanyl)phenylboronic esters, iodo(pentafluorosulfanyl)benzenes and (pentafluorosulfanyl)benzene is shown.
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http://dx.doi.org/10.3762/bjoc.11.162 | DOI Listing |
Nanoscale
September 2020
Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
The chemistry of carbon surfaces has regained traction in recent years in view of its applicability towards covalent modification of a variety of (2D) materials. A general requisite is the formation of a dense and well-defined monolayer of aryl groups covalently bound to the surface. Given the use of reactive chemistries however, it is often not easy to achieve precise control over the monolayer growth while maintaining high grafting densities.
View Article and Find Full Text PDFNanoscale
June 2020
Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
Covalent functionalization of graphene is highly sought after, not only in view of the potential applications of the chemically modified material, but also because it brings fundamental insight into the chemistry of graphene. Thus, strategies that yield chemically modified graphene with densely grafted films of aryl groups via simple experimental protocols have been the focus of intense research. Here we report a mild, straightforward and efficient approach to graphene/graphite functionalization using iodide mediated reductive dediazoniation of aryldiazonium salts.
View Article and Find Full Text PDFChem Sci
September 2016
Department of Chemistry , University of South Florida, Tampa , FL 33620 , USA . Email:
Gold-catalyzed C-heteroatom (C-X) coupling reactions are evaluated without using sacrificial oxidants. Vital to the success of this methodology is the nucleophile-assisted activation of aryldiazonium salts, which could be an effective oxidant for converting Au(i) to Au(iii) even without the addition of an assisting ligand or photocatalyst. By accelerating the reaction kinetics to outcompete C-C homo-coupling or diazonium dediazoniation, gold-catalyzed Sandmeyer reactions were achieved with different nucleophiles, forming C-Br, C-S and C-P bonds in high yields and selectivities.
View Article and Find Full Text PDFBeilstein J Org Chem
October 2015
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague 6, Czech Republic.
Pyridine promotes dediazoniation of aryldiazonium tetrafluoroborates. The formed aryl radicals were trapped with B2pin2, iodine, or tetrahydrofuran to afford boronic esters, iodobenzenes and benzenes, respectively. The application to the synthesis of (pentafluorosulfanyl)phenylboronic esters, iodo(pentafluorosulfanyl)benzenes and (pentafluorosulfanyl)benzene is shown.
View Article and Find Full Text PDFJ Org Chem
September 2015
Institute für Physikalische und Theoretischen Chemie, University of Regensburg, 93053 Regensburg, Germany.
The dediazoniation of aryldiazonium salts in mixed solvents proceeds by a borderline SN1 and SN2 pathway, and product distribution should be proportional to the composition of the solvation shell of the carbon attached to the -N2 group (ipso carbon). The rates of dediazoniation of 2,4,6-trimethylbenzenediazonium in water, methanol, ethanol, propanol, and acetonitrile were similar, but measured product distributions were noticeably dependent on the nature of the water/cosolvent mixture. Here we demonstrated that solvent distribution in the first solvation shell of the ipso carbon, calculated from classical molecular dynamics simulations, is equal to the measured product distribution.
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