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Diaryliodonium Salts: Synthesis, Applications and Computational Investigations
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Berit Olofsson)
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 [en]
diaryliodonium salt, hypervalent iodine, density functional theory, aryne, phenol, nitroarene
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-162326ISBN: 978-91-7797-398-0 (print)ISBN: 978-91-7797-399-7 (electronic)OAI: oai:DiVA.org:su-162326DiVA, id: diva2:1265728
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
List of papers
1. One-Pot Synthesis of Unsymmetric Diaryliodonium Salts from Iodine and Arenes
Open this publication in new window or tab >>One-Pot Synthesis of Unsymmetric Diaryliodonium Salts from Iodine and Arenes
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.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-149793 (URN)10.1021/acs.joc.7b01652 (DOI)000416204400033 ()28809562 (PubMedID)
Funder
Swedish Research Council
Available from: 2017-12-19 Created: 2017-12-19 Last updated: 2018-11-26Bibliographically approved
2. One-Pot C-H Functionalization of Arenes by Diaryliodonium Salts
Open this publication in new window or tab >>One-Pot C-H Functionalization of Arenes by Diaryliodonium Salts
2016 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 55, no 31, p. 8928-8932Article in journal (Refereed) Published
Abstract [en]

A transition-metal-free, mild, and highly regioselective synthesis of nitroarenes from arenes has been developed. The products are obtained in a sequential one-pot reaction by nitration of iodine(III) reagents with two carbon ligands, which are formed in situ from iodine(I). This novel concept has been extended to formation of aryl azides, and constitutes an important step towards catalytic reactions with these hypervalent iodine reagents. An efficient nitration of isolated diaryl-iodonium salts has also been developed, and the mechanism is proposed to proceed by a [2,2] ligand coupling pathway.

Keywords
arylation, density functional calculations, hypervalent compounds, oxidation, reaction mechanisms
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-135133 (URN)10.1002/anie.201603175 (DOI)000383253700022 ()27272891 (PubMedID)
Funder
Swedish Research Council
Available from: 2016-11-01 Created: 2016-10-31 Last updated: 2018-11-26Bibliographically approved
3. Competing Pathways in O-Arylations with Diaryliodonium Salts: Mechanistic Insights
Open this publication in new window or tab >>Competing Pathways in O-Arylations with Diaryliodonium Salts: Mechanistic Insights
Show others...
2017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 53, p. 13249-13258Article in journal (Refereed) Published
Abstract [en]

A mechanistic study of arylations of aliphatic alcohols and hydroxide with diaryliodonium salts, to give alkyl aryl ethers and diaryl ethers, has been performed using experimental techniques and DFT calculations. Aryne intermediates have been trapped, and additives to avoid by-product formation originating from arynes have been found. An alcohol oxidation pathway was observed in parallel to arylation; this is suggested to proceed by an intramolecular mechanism. Product formation pathways via ligand coupling and arynes have been compared, and 4-coordinated transition states were found to be favored in reactions with alcohols. Furthermore, a novel, direct nucleophilic substitution pathway has been identified in reactions with electron-deficient diaryliodonium salts.

Keywords
aryl ethers, arynes, hypervalent iodine, mechanistic study, oxidation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-148082 (URN)10.1002/chem.201703057 (DOI)000411357000038 ()28792102 (PubMedID)
Available from: 2017-10-24 Created: 2017-10-24 Last updated: 2018-11-26Bibliographically approved
4. Synthesis of Phenols and Aryl Silyl Ethers via Arylation of Complementary Hydroxide Surrogates
Open this publication in new window or tab >>Synthesis of Phenols and Aryl Silyl Ethers via Arylation of Complementary Hydroxide Surrogates
Show others...
2018 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 20, no 7, p. 1785-1788Article in journal (Refereed) Published
Abstract [en]

Two transition-metal-free methods to access substituted phenols via the arylation of silanols or hydrogen peroxide with diaryliodonium salts are presented. The complementary reactivity of the two nucleophiles allows synthesis of a broad range of phenols without competing aryne formation, as illustrated by the synthesis of the anesthetic Propofol. Furthermore, silyl-protected phenols can easily be obtained, which are suitable for further transformations.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-155954 (URN)10.1021/acs.orglett.8b00287 (DOI)000429886900022 ()29537280 (PubMedID)
Available from: 2018-05-21 Created: 2018-05-21 Last updated: 2018-11-26Bibliographically approved

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