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Development and Applications of Hypervalent Iodine Compounds: Powerful Arylation and Oxidation Reagents
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The first part of this thesis describes the efficient synthesis of several hypervalent iodine(III) compounds. Electron-rich diaryliodonium salts have been synthesized in a one-pot procedure, employing mCPBA as the oxidant. Both symmetric and unsymmetric diaryliodonium tosylates can be isolated in high yields. An in situ anion exchange also enables the synthesis of previously unobtainable diaryliodonium triflates.

A large-scale protocol for the synthesis of a derivative of Koser’s reagent, that is an isolable intermediate in the diaryliodonium tosylate synthesis, is furthermore described. The large-scale synthesis is performed in neat TFE, which can be recovered and recycled. This is very desirable from an environmental point of view.

One of the few described syntheses of enantiopure diaryliodonium salts is discussed. Three different enantiopure diaryliodonium salts bearing electron-rich substituents are synthesized in moderate to high yields. The synthesis of these three salts shows the challenge in the preparation of electron-rich substituted unsymmetric salts.

The second part of the thesis describes the application of both symmetric and unsymmetric diaryliodonium salts in organic synthesis. A metal-free efficient and fast method for the synthesis of diaryl ethers from diaryliodonium salts has been developed. The substrate scope is wide as both the phenol and the diaryliodonium salt can be varied. Products such as halogenated ethers, ortho-substituted ethers and bulky ethers, that are difficult to obtain with metal-catalyzed procedures, are readily prepared. The mild protocol allows arylation of racemization-prone a-amino acid derivatives without loss of enantiomeric excess.

A chemoselectivity investigation was conducted, in which unsymmetric diaryliodonium salts were employed in the arylation of three different nucleophiles in order to understand the different factors that influence which aryl moiety that is transferred to the nucleophile.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2012. , 71 p.
Keyword [en]
hypervalent iodine compounds, diaryliodonium salts, oxidation, Koser's reagent, arylation, phenols, diaryl ethers, chemoselectivity
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-75810ISBN: 978-91-7447-505-0 (print)OAI: oai:DiVA.org:su-75810DiVA: diva2:524057
Public defence
2012-06-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Accepted. Paper 5: Submitted. Paper 6: Manuscript.

Available from: 2012-05-10 Created: 2012-04-27 Last updated: 2013-08-09Bibliographically approved
List of papers
1. One-pot synthesis of diaryliodonium salts using toluenesulfonic acid - a fast entry to electron-rich diaryliodonium tosylates and triflates
Open this publication in new window or tab >>One-pot synthesis of diaryliodonium salts using toluenesulfonic acid - a fast entry to electron-rich diaryliodonium tosylates and triflates
2008 (English)In: Synlett: Accounts and Rapid Communications in Synthetic Organic Chemistry, ISSN 0936-5214, E-ISSN 1437-2096, no 4, 592-596 p.Article in journal (Refereed) Published
Abstract [en]

A direct synthesis of symmetric and unsymmetric electron-rich diaryliodonium salts is described. The use of MCPBA and toluenesulfonic acid delivers diaryliodonium tosylates in high yields. An in situ anion exchange has also been developed, giving access to the corresponding triflate salts.

Keyword
hypervalent iodine, diaryliodonium salts, oxidations, arenes, electrophilic aromatic substitution
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-14044 (URN)10.1055/s-2008-1032050 (DOI)000254242500025 ()
Funder
Swedish Research Council, 621-2006-4027
Available from: 2009-01-05 Created: 2009-01-05 Last updated: 2014-10-29Bibliographically approved
2. Synthesis of Koser’s Reagent and Derivatives
Open this publication in new window or tab >>Synthesis of Koser’s Reagent and Derivatives
2013 (English)In: Organic Syntheses, ISSN 0078-6209, Vol. 90, 1-9 p.Article in journal (Refereed) Published
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-75776 (URN)
Funder
Swedish Research Council, 621-2011-3608
Available from: 2012-04-26 Created: 2012-04-26 Last updated: 2017-12-07Bibliographically approved
3. Design and asymmetric synthesis of chiral diaryliodonium salts
Open this publication in new window or tab >>Design and asymmetric synthesis of chiral diaryliodonium salts
2010 (English)In: Tetrahedron, ISSN 0040-4020, E-ISSN 1464-5416, Vol. 66, no 31, 5793-5800 p.Article in journal (Refereed) Published
Abstract [en]

The application of chiral hypervalent iodine reagents in asymmetric synthesis is highly desirable, as the reagents are metal-free, environmentally benign and employed under mild conditions. Three chiral diaryliodonium salts have been designed to provide chemoselectivity and asymmetric induction in asymmetric alpha-phenylation of carbonyl compounds. The synthetic routes to the selected targets are detailed herein, together with a structural investigation into the diastereoselectivity of the alkylation process.

Keyword
Hypervalent iodine, Diaryl-[lambda]3-iodanes, Asymmetric synthesis, Oxidation, Arylation reagents
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-43501 (URN)10.1016/j.tet.2010.05.004 (DOI)000280344200009 ()
Funder
Swedish Research Council, 621-2008-3709
Available from: 2010-10-18 Created: 2010-10-18 Last updated: 2017-12-12Bibliographically approved
4. Room temperature, metal-free synthesis of diaryl ethers with use of diaryliodonium salts
Open this publication in new window or tab >>Room temperature, metal-free synthesis of diaryl ethers with use of diaryliodonium salts
2011 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 13, no 6, 1552-1555 p.Article in journal (Refereed) Published
Abstract [en]

A fast, high-yielding synthesis of diaryl ethers with use of mild and metal-free conditions has been developed. The scope includes bulky orthosubstituteddiaryl ethers, which are difficult to obtain by metal-catalyzed protocols. Halo-substituents, racemization-prone amino acid derivatives,and heteroaromatics are also tolerated. The methodology is expected to be of high utility in the synthesis of complex molecules and in thepharmaceutical industry.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-59890 (URN)10.1021/ol200265t (DOI)000288148800074 ()
Funder
Swedish Research Council, 621-2008-3709
Available from: 2011-07-25 Created: 2011-07-25 Last updated: 2017-12-08Bibliographically approved
5. Metal-Free Arylation of Oxygen Nucleophiles with Diaryliodonium Salts
Open this publication in new window or tab >>Metal-Free Arylation of Oxygen Nucleophiles with Diaryliodonium Salts
2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 44, 14140-14149 p.Article in journal (Refereed) Published
Abstract [en]

Phenols and carboxylic acids are efficiently arylated with diaryliodonium salts. The reaction conditions are mild, metal free, and avoid the use of halogenated solvents, additives, and excess reagents. The products are obtained in good-to-excellent yields after short reaction times. Steric hindrance is very well tolerated, both in the nucleophile and diaryliodonium salt. The scope includes ortho-and halo-substituted products, which are difficult to obtain by metal-catalyzed protocols. Many functional groups are tolerated, including carbonyl groups, heteroatoms, and alkenes. Unsymmetric salts can be chemoselectively utilized to obtain products with hitherto unreported levels of steric congestion. The arylation has been extended to sulfonic acids, which can be converted to sulfonate esters by two different approaches. With recent advances in efficient synthetic procedures for diaryliodonium salts the reagents are now inexpensive and readily available. The iodoarene byproduct formed from the iodonium reagent can be recovered quantitatively and used to regenerate the diaryliodonium salt, which improves the atom economy.

Keyword
aryl esters, arylation, diaryl ethers, hypervalent iodine, synthetic methods
National Category
Chemical Sciences Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-82958 (URN)10.1002/chem.201201645 (DOI)000310473900031 ()
Funder
Swedish Research Council, 621-2008-3709Carl Tryggers foundation , 08:288Carl Tryggers foundation , 09:281
Note

AuthorCount:3;

Available from: 2012-12-14 Created: 2012-12-03 Last updated: 2017-12-06Bibliographically approved
6. Arylation with Unsymmetrical Diaryliodonium Salts: A Chemoselectivity Study
Open this publication in new window or tab >>Arylation with Unsymmetrical Diaryliodonium Salts: A Chemoselectivity Study
Show others...
2013 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 19, no 31, 10334-10342 p.Article in journal (Refereed) Published
Abstract [en]

Phenols, anilines, and malonates have been arylated under metal-free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new “anti-ortho effect” has been identified in the arylation of malonates. Several “dummy groups” have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal-free reagents.

Keyword
arylation, chemoselectivity, DFT calculations, hypervalent compounds, ligand exchange
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-75778 (URN)10.1002/chem.201300860 (DOI)000321983700034 ()
Funder
Swedish Research Council, 621-2011-3608
Available from: 2012-04-26 Created: 2012-04-26 Last updated: 2017-12-07Bibliographically approved

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