Skip to content
Research Article Open access CC BY 4.0

An Unexpected Reaction between Diaryliodonium Salts and DMSO

Konrad Kepski, Wesley James Moran

Organics · pp. 275–280 · Published 31 Aug 2022

10.3390/org3030020

Abstract

Diaryliodonium salts are useful arylating reagents that have been exploited widely. In this Communication, we demonstrate that heating diphenyliodonium triflate in the solvent DMSO leads to an unexpected arylation reaction. It is postulated that arylation of DMSO at oxygen, followed by a thia-Sommelet–Hauser rearrangement, leads to the formation of 2-thiomethylphenols. More substituted diaryliodonium salts and cyclic diaryliodonium salts are shown to be more stable and less likely to react with DMSO. In conclusion, when using iodonium salts dissolved in DMSO, beware of side-reactions.

Reagent Solvent Chemistry Trifluoromethanesulfonate Combinatorial chemistry Oxygen Reaction conditions Organic chemistry

References (24)

  1. 1 Pacheco-Benichou, A., Besson, T., and Fruit, C. (2020). Diaryliodoniums Salts as Coupling Partners for Transition-Metal Catalyzed C- and N-Arylation of Heteroarenes. Catalysts, 10. [DOI]
  2. 2 Zhichao, 2013, Progresses of Diaryliodonium Salts in Organic Reactions [DOI]
  3. 3 Merritt, 2009, Diaryliodonium Salts: A Journey from Obscurity to Fame [DOI]
  4. 4 Grushin, 2000, Cyclic diaryliodonium ions: Old mysteries solved and new applications envisaged [DOI]
  5. 5 Shetgaonkar, S.E., Mamgain, R., Kikushima, K., Dohi, T., and Singh, F.V. (2022). Palladium-Catalyzed Organic Reactions Involving Hypervalent Iodine Reagents. Molecules, 27. [DOI]
  6. 6 Shetgaonkar, 2022, Non-Palladium-Catalyzed Oxidative Coupling Reactions Using Hypervalent Iodine Reagents [DOI]
  7. 7 Stuart, 2017, Aryl Transfer Selectivity in Metal-Free Reactions of Unsymmetrical Diaryliodonium Salts [DOI]
  8. 8 Zawia, E., and Moran, W.J. (2016). Aqueous DMSO Mediated Conversion of (2-(Arylsulfonyl)vinyl)iodonium Salts to Aldehydes and Vinyl Chlorides. Molecules, 21. [DOI]
  9. 9 Breugst, 2012, Nucleophilic Reactivities of the Anions of Nucleobases and Their Subunits [DOI]
  10. 10 Appel, 2010, Nucleophilic Reactivities of Sulfur Ylides and Related Carbanions: Comparison with Structurally Related Organophosphorus Compounds [DOI]
  11. 11 Mancuso, 1981, Activated Dimethyl Sulfoxide: Useful Reagents for Synthesis [DOI]
  12. 12 Wan, 2022, Reactions of Sulfoxides with Benzynes [DOI]
  13. 13 Sundalam, 2016, A Selective C−H Deprotonation Strategy to Access Functionalized Arynes by Using Hypervalent Iodine [DOI]
  14. 14 Wang, 2016, Transition metal-free N-arylation of secondary amides through iodonium salts as aryne precursors [DOI]
  15. 15 Stuart, 2017, Unsymmetrical Diaryliodonium Salts as Aryne Synthons: Renaissance of a C−H Deprotonative Approach to Arynes [DOI]
  16. 16 Nilova, 2021, Regioselective Synthesis of 1,2,3,4-Tetrasubstituted Arenes by Vicinal Functionalization of Arynes Derived from Aryl(Mes)iodonium Salts [DOI]
  17. 17 Saikia, 2022, Metal-free S-arylation of 5-mercaptotetrazoles and 2-mercaptopyridine with unsymmetrical diaryliodonium salts [DOI]
  18. 18 Bur, 2004, The Pummerer Reaction:  Methodology and Strategy for the Synthesis of Heterocyclic Compounds [DOI]
  19. 19 Higuchi, 2021, The Interrupted Pummerer Reaction: Design of Sulfoxides and their Utility in Organic Synthesis [DOI]
  20. 20 Lin, 2019, Asymmetric Catalytic [2,3] Stevens and Sommelet–Hauser Rearrangements of α-Diazo Pyrazoleamides with Sulfides [DOI]
  21. 21 Elsherbini, 2021, Scalable electrochemical synthesis of diaryliodonium salts [DOI]
  22. 22 Li, 2020, Molecular tuning of CO2-to-ethylene conversion [DOI]
  23. 23 Mayer, 2020, Lewis Acidity Scale of Diaryliodonium Ions toward Oxygen, Nitrogen and Halogen Lewis Bases [DOI]
  24. 24 Koseki, 2019, Efficient N-arylation of azole compounds utilizing selective aryl-transfer TMP-iodonium(III) reagents [DOI]

Cited by 8

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

Ritu Mamgain, Kokila Sakthivel, Fateh Veer Singh · Beilstein Journal of Organic Chemistry · 2024

Showing 4 of 8 known citations — external sources report more than can currently be individually listed.

Article metrics

Real usage data collected on this platform.

0

Page views

0

PDF downloads

0

Outbound clicks

8

Citations

Views by country

Approximate, from request IP at view time — not citizenship or institution. Countries with fewer than 5 views are grouped as "Other".

No views recorded yet.

Traffic sources

Referring site, by host.

No traffic recorded yet.

Views and downloads exclude known bots/crawlers. Citations combines this platform's own DOI-resolved index with each external source's own reported total — see Cited by above for individually listed citing works. Last refreshed 0 seconds ago.