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Diaryliodonium Salts: Development of Synthetic Methodologies and α-Arylation of Enolates
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Berit Olofsson)
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes novel reaction protocols for the synthesis of diaryliodonium salts and also provides an insight to the mechanism of α-arylation of carbonyl compounds with diaryliodonium salts.

 The first chapter gives a general introduction to the field of hypervalent iodine chemistry, mainly focusing on recent developments and applications of diaryliodonium salts.

Chapter two describes the synthesis of electron-rich to electron-poor diaryliodonium triflates, in moderate to excellent yields from a range of arenes and iodoarenes.

In chapter three, it is described that molecular iodine can be used together with arenes in a direct one-pot, three-step synthesis of symmetric diaryliodonium triflates. A large scale synthesis of bis(4-tert-butylphenyl)iodonium triflate is also described, controlled and verified by an external research group, further demonstrating the reliability of this methodology.

The fourth chapter describes the development of a sequential one-pot synthesis of diaryliodonium salts from aryl iodides and boronic acids, furnishing symmetric and unsymmetric, electron-rich to electron-poor diaryliodonium tetrafluoroborates in moderate to excellent yields. This method was developed to overcome the regiochemical limitations imposed by the reaction mechanism in the protocols described in the preceding chapters.

Chapter five describes a one-pot synthesis of heteroaromatic iodonium salts under similar conditions described in chapter two.

The final chapter describes the reaction of enolates with chiral diaryliodonium salts or together with a phase transfer catalyst yielding racemic products. DFT calculations were performed, which revealed a low lying energy transition state (TS) between intermediates, which is believed to be responsible for the lack of selectivity observed in the experimental work. It is also proposed that a [2,3] rearrangement is preferred over a [1,2] rearrangement in the α-arylation of carbonyl compounds.

The synthetic methodology described in this thesis is the most generally applicable, efficient and high-yielding to date for the synthesis of diaryliodonium salts, making these reagents readily available for various applications in synthesis.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2011. , 88 p.
Keyword [en]
Hypervalent Iodine Compounds, One-Pot Synthesis, Regiospecific Synthesis, Aromatic Substitution, Aryl Iodides, Arenes, Boronic Acids, Heteroaromatics, Arylations, Reaction Mechanisms, Density Functional Calculations, Large Scale Synthesis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-54738ISBN: 978-91-7447-233-2OAI: oai:DiVA.org:su-54738DiVA: diva2:403072
Public defence
2011-04-15, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2011-03-24 Created: 2011-02-14 Last updated: 2011-06-09Bibliographically approved
List of papers
1. High-Yielding One-Pot Synthesis of Diaryliodonium Triflates from Arenes and Iodine or Aryl Iodides
Open this publication in new window or tab >>High-Yielding One-Pot Synthesis of Diaryliodonium Triflates from Arenes and Iodine or Aryl Iodides
2007 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, no 24, 2521-2523 p.Article in journal (Refereed) Published
Abstract [en]

Unsymmetric and symmetric diaryliodonium triflates are synthesized from both electron-deficient and electron-rich substrates in a fast, high yielding, and operationally simple protocol employing arenes and aryl iodides or iodine.

National Category
Inorganic Chemistry Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-25299 (URN)10.1039/b701864a (DOI)
Available from: 2008-06-16 Created: 2008-06-16 Last updated: 2015-03-21Bibliographically approved
2. Efficient and General One-Pot Synthesis of Diaryliodonium Triflates: Optimization, Scope and Limitations
Open this publication in new window or tab >>Efficient and General One-Pot Synthesis of Diaryliodonium Triflates: Optimization, Scope and Limitations
2007 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 349, no 17-18, 2610-2618 p.Article in journal (Refereed) Published
Abstract [en]

Symmetrical and unsymmetrical diaryliodonium triflates have been synthesized from both electron-deficient and electron-rich arenes and aryl iodides with mCPBA and triflic acid. A thorough investigation of the optimization, scope and limitations has resulted in an improved one-pot protocol that is fast, high-yielding, and operationally simple. The reaction has been extended to the direct synthesis of symmetrical iodonium salts from iodine and arenes, conveniently circumventing the need for aryl iodides.

Keyword
arenes, aromatic substitution, diaryliodonium salts, hypervalent compounds, iodine, oxidation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-25300 (URN)10.1002/adsc.200700373 (DOI)000251737500011 ()
Funder
Swedish Research Council, 621-2006-4027
Available from: 2008-06-16 Created: 2008-06-16 Last updated: 2015-10-13Bibliographically approved
3. Efficient one-pot synthesis of bis(4-tert-butylphenyl)iodonium triflate
Open this publication in new window or tab >>Efficient one-pot synthesis of bis(4-tert-butylphenyl)iodonium triflate
2009 (English)In: Organic Syntheses, ISSN 0078-6209, Vol. 86, 308-314 p.Article in journal (Refereed) Published
National Category
Other Basic Medicine Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-29390 (URN)10.1002/0471264229.os086.29 (DOI)
Funder
Swedish Research Council, 621-2006-4027
Note

Published on the Web 6/16/2009

Available from: 2010-01-04 Created: 2009-08-26 Last updated: 2015-10-16Bibliographically approved
4. Regiospecific One-Pot Synthesis of Diaryliodonium Tetrafluoroborates from Arylboronic Acids and Aryl Iodides
Open this publication in new window or tab >>Regiospecific One-Pot Synthesis of Diaryliodonium Tetrafluoroborates from Arylboronic Acids and Aryl Iodides
2008 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 73, no 12, 4602-4607 p.Article in journal (Refereed) Published
Abstract [en]

Diaryliodonium salts have recently received considerable attention as mild arylation reagents in organic synthesis. This paper describes a regiospecific, sequential one-pot synthesis of symmetrical and unsymmetrical diaryliodonium tetrafluoroborates, which are the most popular salts in metal-catalyzed arylations. The protocol is fast and high-yielding and has a large substrate scope. Furthermore, the corresponding diaryliodonium triflates can conveniently be obtained via an in situ anion exchange.

Keyword
diaryliodonium salts, MCPBA
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-25301 (URN)10.1021/jo8004974 (DOI)000256757100030 ()
Funder
Swedish Research Council, 621-2006-4027
Available from: 2008-06-16 Created: 2008-06-16 Last updated: 2015-10-27Bibliographically approved
5. α-Arylation by Rearrangement: On the Reaction of Enolates with Diaryliodonium Salts
Open this publication in new window or tab >>α-Arylation by Rearrangement: On the Reaction of Enolates with Diaryliodonium Salts
2010 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 16, no 28, 8251-8254 p.Article in journal (Refereed) Published
Abstract [en]

Surprising equilibration: A new mechanism for the title reaction is supported by DFT calculations and experimental observations. The CI and OI intermediates are isoenergetic and equilibrate quickly. Thus, any chiral information induced in the initial complex will be destroyed. In the final CC bond-forming step, a [2,3]-rearrangement from the OI bonded intermediate is slightly preferred over the [1,2]-elimination from the CI bonded isomer (see scheme).

Keyword
arylation, density functional calculations, hypervalent compounds, iodanes, reaction mechanisms
National Category
Chemical Sciences Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-50196 (URN)10.1002/chem.201001110 (DOI)000280819100003 ()
Funder
Swedish Research Council, 621-2008-3709Carl Tryggers foundation , 08:288Carl Tryggers foundation , 09:281Knut and Alice Wallenberg Foundation
Note

authorCount :4

Available from: 2010-12-21 Created: 2010-12-21 Last updated: 2015-09-22Bibliographically approved

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