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Efficient and General One-Pot Synthesis of Diaryliodonium Triflates: Optimization, Scope and Limitations
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.
Responsible organisation
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.

Place, publisher, year, edition, pages
2007. Vol. 349, no 17-18, 2610-2618 p.
Keyword [en]
arenes, aromatic substitution, diaryliodonium salts, hypervalent compounds, iodine, oxidation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-25300DOI: 10.1002/adsc.200700373ISI: 000251737500011OAI: oai:DiVA.org:su-25300DiVA: diva2:199370
Funder
Swedish Research Council, 621-2006-4027
Available from: 2008-06-16 Created: 2008-06-16 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Efficient and High-Yielding Routes to Diaryliodonium Salts
Open this publication in new window or tab >>Efficient and High-Yielding Routes to Diaryliodonium Salts
2008 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis summarizes three novel and general reaction protocols for the synthesis of diaryliodonium salts. All protocols utilize mCPBA as oxidant and the acids used are either TfOH, to obtain triflate salts, or BF3•Et2O that gives the corresponding tetrafluoroborate salts in situ.

Chapter two describes the reaction of various arenes and aryl iodides, delivering electron-rich and electron-deficient triflates in moderate to excellent yields.

In chapter three, it is shown that the need of aryl iodides can be circumvented, as molecular iodine can be used together with arenes in a direct one-pot, three-step synthesis of symmetric diaryliodonium triflates.

The final and fourth chapter describes the development of a sequential one-pot reaction from aryl iodides and boronic acids, delivering symmetric and unsymmetric, electron-rich and electron-deficient iodonium tetrafluoroborates in moderate to excellent yields. This protocol was developed to overcome mechanistic limitations existing in the protocols described in chapter two and three.

The methodology described in this thesis is the most general, efficient and high-yielding existing up to date, making diaryliodonium salts easily available for various applications in synthesis.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2008. 49 p.
Keyword
Hypervalent Iodine Compounds, One-Pot Synthesis, Regiospecific Synthesis, Aromatic Substitution, Aryl Iodides, Arenes, Boronic Acids
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-7969 (URN)978-91-7155-686-8 (ISBN)
Presentation
2008-06-25, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00
Supervisors
Available from: 2008-06-16 Created: 2008-06-16 Last updated: 2011-03-17Bibliographically approved
2. Diaryliodonium Salts: Development of Synthetic Methodologies and α-Arylation of Enolates
Open this publication in new window or tab >>Diaryliodonium Salts: Development of Synthetic Methodologies and α-Arylation of Enolates
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
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:nbn:se:su:diva-54738 (URN)978-91-7447-233-2 (ISBN)
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

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