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One-Pot Synthesis of Unsymmetric Diaryliodonium Salts from Iodine and Arenes
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0001-7975-4582
2017 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 82, no 22, p. 11909-11914Article in journal (Refereed) Published
Abstract [en]

The first synthesis of unsymmetric diaryliodonium salts directly from iodine and arenes is presented. The methodology provides diaryliodonium salts with the trimethoxyphenyl (TMP) moiety as dummy group. The protocol avoids the customary use of iodoarenes, which can be both expensive and toxic. Excess reagents are not required, and the reactions are performed under mild conditions. O-Arylations with these TMP salts were demonstrated to be highly chemoselective.

Place, publisher, year, edition, pages
2017. Vol. 82, no 22, p. 11909-11914
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-149793DOI: 10.1021/acs.joc.7b01652ISI: 000416204400033PubMedID: 28809562OAI: oai:DiVA.org:su-149793DiVA, id: diva2:1167806
Funder
Swedish Research CouncilAvailable from: 2017-12-19 Created: 2017-12-19 Last updated: 2018-11-26Bibliographically approved
In thesis
1. Diaryliodonium Salts: Synthesis, Applications and Computational Investigations
Open this publication in new window or tab >>Diaryliodonium Salts: Synthesis, Applications and Computational Investigations
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Organic chemists have the ability to create complex organic molecules by connecting molecular building blocks in different ways. To name a few, these molecules are used as medicines, pesticides or in our household electronics, and are therefore crucial to life as we know it. While many excellent methods for the connection of these fragments are known, serious issues regarding efficiency and sustainability remain. Our research concerns the use of diaryliodonium salts as a way of improving on these issues. Diaryliodonium salts are hypervalent iodine reagents used to transfer aryl groups to suitable nucleophiles. This thesis concerns the synthesis of these reagents and their use in the formation of carbon-nitrogen and carbon-oxygen bonds.

The first project investigates the possibility to synthesize unsymmetrical diaryliodonium salts starting from elemental iodine and arenes, as such a method could be more cost efficient and sustainable compared to existing methods starting from iodoarenes. It was found that highly sterically congested diaryliodonium salts could be synthesized in high yields.

Next, we applied diaryliodonium salts in the arylation of nitrite to form aromatic nitro compounds. The methodology offered a broad scope with good to excellent yields. Furthermore, we presented the in situ functionalization of diaryliodonium salts that had been formed from iodoarenes and arenes. This conceptually novel approach could be a step towards a catalytic reaction using diaryliodonium salts.

In the third project we investigated the mechanisms of O-arylations with diaryliodonium salts to provide a deeper understanding of the reaction pathways involved in product and byproduct formation. Reactions between electron-rich diaryliodonium salts, hydroxides or secondary alcohols were studied.  When using hydroxide as the nucleophile, the side products could be suppressed by the addition of aryne traps, suggesting such an intermediate in the reaction. A novel mechanism for the formation of the aryne was proposed based on DFT calculations.  When alcohols were used we detected the oxidation of the alcohol rather than aryne products. The oxidized product was shown to not originate from arynes or a radical process but was formed via an intramolecular deprotonation from a 4-coordinated intermediate as suggested by DFT-calculations and experiments.

In the final project we developed two complementary methods for the synthesis of phenols using hydroxide surrogates as nucleophiles. These compounds have previously been difficult to make using diaryliodonium salts due to aryne formation or overarylation to form diaryl ethers. The first method used hydrogen peroxide as the surrogate and allowed formation of electron-deficient and moderately electron-rich phenols. The synthesis of ortho-alkyl substituted phenols could be accomplished by using silanols as the surrogate. This allowed us to synthesize several highly congested phenols in good yields. Highly electron-rich diaryliodonium salts were, however, not compatible with either of the two methods.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2019. p. 70
Keywords
diaryliodonium salt, hypervalent iodine, density functional theory, aryne, phenol, nitroarene
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-162326 (URN)978-91-7797-398-0 (ISBN)978-91-7797-399-7 (ISBN)
Public defence
2019-01-11, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2018-12-17 Created: 2018-11-26 Last updated: 2018-12-07Bibliographically approved

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