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Metal-Free O- and C-Arylation with Diaryliodonium Salts
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Berit Olofsson)
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis concerns the development of metal-free applications using diaryliodonium salts. The first project describes an arylation protocol of allylic and benzylic alcohols in aqueous media. The method proceeds under mild conditions and the ether products were obtained in moderate to good yields. The methodology was also expanded to include arylation of phenols, giving diaryl ethers in good to excellent yields. In the second project, an arylation method that included a wider range of aliphatic alcohols was developed. The scope of accessible alkyl aryl ethers was studied and included a comparative study of phenylation and nitrophenylation of various alcohols. Finally, a formal metal-free synthesis of butoxycain was performed, illustrating the applicability of the developed method.

The third project focused on the limitations and side reactions occurring in Chapter 2 and 3. First, an approach to access symmetric diaryl ethers via arylation of hydroxide was presented. This reaction gave rise to a number of side products, which we hypothesized to originate from aryne-type intermediates. A mechanism for the formation of these side products was suggested, supported by trapping and deuterium labeling experiments.

Oxidation of the alcohol to the corresponding ketone was also observed and the mechanism of this interesting side reaction was investigated. The latter was suggested to proceed via an intramolecular oxidation without the involvement of radicals or arynes.

The fourth project covers a method to synthesize highly sterically congested alkyl aryl ethers via arylation of tertiary alcohols using diaryliodonium salts. The method displayed a broad scope of tertiary alcohols and was also suitable for fluorinated alcohols.

The final project detailed in this thesis deals with C-arylation with diaryliodonium salts, showcasing nitroalkanes as well as a nitro ester as suitable nucleophiles for metal-free arylation. 

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2017. , p. 85
Keywords [en]
Hypervalent Iodine, Alkyl Aryl Ethers, Nitro Compounds, Alcohols, Diaryliodonium Salts
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-140944ISBN: 978-91-7649-702-9 (print)ISBN: 978-91-7649-703-6 (electronic)OAI: oai:DiVA.org:su-140944DiVA, id: diva2:1084266
Public defence
2017-05-12, Magnélisalen, Kemiska Övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.

Available from: 2017-04-19 Created: 2017-03-24 Last updated: 2018-02-20Bibliographically approved
List of papers
1. Metal-Free Synthesis of Aryl Ethers in Water
Open this publication in new window or tab >>Metal-Free Synthesis of Aryl Ethers in Water
2013 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 15, no 23, p. 6070-6073Article in journal (Refereed) Published
Abstract [en]

The first arylation of allylic and benzylic alcohols with diaryliodonium salts is reported. The reaction yields alkyl aryl ethers under mild and metal-free conditions. Phenols are arylated to diaryl ethers in good to excellent yields. The reaction employs diaryliodonium salts and sodium hydroxide in water at low temperature, and excess amounts of the coupling partners are avoided.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-98274 (URN)10.1021/ol402960f (DOI)000328231500042 ()
Funder
Swedish Research Council, 621-2011-3608
Note

AuthorCount:3;

Available from: 2014-01-09 Created: 2014-01-03 Last updated: 2017-12-06Bibliographically approved
2. Room Temperature, Metal-Free Arylation of Aliphatic Alcohols
Open this publication in new window or tab >>Room Temperature, Metal-Free Arylation of Aliphatic Alcohols
2014 (English)In: ChemistryOpen, ISSN 2191-1363, Vol. 3, no 2, p. 54-57Article in journal (Refereed) Published
Abstract [en]

Diaryliodonium salts are demonstrated as efficient arylating agents of aliphatic alcohols under metal-free conditions. The reaction proceeds at room temperature within 90min to give alkyl aryl ethers in good to excellent yields. Aryl groups with electron-withdrawing substituents are transferred most efficiently, and unsymmetric iodonium salts give chemoselective arylations. The methodology has been applied to the formal synthesis of butoxycaine.

Keywords
aliphatic alcohols, alkyl aryl ethers, arylation, diaryliodonium salts, hypervalent iodine
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-103962 (URN)10.1002/open.201402006 (DOI)000334680800002 ()
Funder
Swedish Research Council, 621-2011-3608Wenner-Gren Foundations
Note

AuthorCount:4;

Available from: 2014-06-09 Created: 2014-05-27 Last updated: 2017-12-05Bibliographically 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: 2018-02-20Bibliographically approved
4. Mild Synthesis of Sterically Congested Alkyl Aryl Ethers
Open this publication in new window or tab >>Mild Synthesis of Sterically Congested Alkyl Aryl Ethers
2016 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 18, no 17, p. 4234-4237Article in journal (Refereed) Published
Abstract [en]

An efficient and transition-metal-free method is presented to access tertiary alkyl aryl ethers by arylation of tertiary alcohols with ortho-substituted diaryliodonium salts. The scope covers cyclic and acyclic aliphatic, benzylic, allylic, and propargylic tertiary alcohols as well as primary and secondary fluorinated alcohols. The methodology gives access to alkyl aryl ethers of previously unprecedented steric congestion. Furthermore, the versatility of the developed procedure was demonstrated by arylation of the pro-drug mestranol.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-135023 (URN)10.1021/acs.orglett.6b01975 (DOI)000382711200022 ()27586361 (PubMedID)
Funder
Swedish Research Council
Available from: 2016-11-10 Created: 2016-10-31 Last updated: 2018-02-12Bibliographically approved
5. Metal-Free C-Arylation of Nitro Compounds with Diaryliodonium Salts
Open this publication in new window or tab >>Metal-Free C-Arylation of Nitro Compounds with Diaryliodonium Salts
2015 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 17, no 18, p. 4554-4557Article in journal (Refereed) Published
Abstract [en]

An efficient, mild, and metal-free arylation of nitro-alkanes with diaryliodonium salts has been developed, giving easy access to tertiary nitro compounds. The reaction proceeds in high yields without the need for excess reagents and can be extended to alpha-arylation of nitroesters. Nitroalkanes were selectively C-arylated in the presence of other easily arylated functional groups, such as phenols and aliphatic alcohols.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-122329 (URN)10.1021/acs.orglett.5b02270 (DOI)000361867800040 ()
Funder
Carl Tryggers foundation
Available from: 2015-12-01 Created: 2015-10-29 Last updated: 2017-12-01Bibliographically approved

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