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Diaryliodonium Salts: Development of Synthetic Methodologies and α-Arylation of Enolates
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi. (Berit Olofsson)
2011 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Stockholm: Department of Organic Chemistry, Stockholm University , 2011. , s. 88
Nyckelord [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
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-54738ISBN: 978-91-7447-233-2 (tryckt)OAI: oai:DiVA.org:su-54738DiVA, id: diva2:403072
Disputation
2011-04-15, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Tillgänglig från: 2011-03-24 Skapad: 2011-02-14 Senast uppdaterad: 2022-02-24Bibliografiskt granskad
Delarbeten
1. High-Yielding One-Pot Synthesis of Diaryliodonium Triflates from Arenes and Iodine or Aryl Iodides
Öppna denna publikation i ny flik eller fönster >>High-Yielding One-Pot Synthesis of Diaryliodonium Triflates from Arenes and Iodine or Aryl Iodides
2007 (Engelska)Ingår i: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, nr 24, s. 2521-2523Artikel i tidskrift (Refereegranskat) 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.

Nationell ämneskategori
Oorganisk kemi Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-25299 (URN)10.1039/b701864a (DOI)
Tillgänglig från: 2008-06-16 Skapad: 2008-06-16 Senast uppdaterad: 2022-02-25Bibliografiskt granskad
2. Efficient and General One-Pot Synthesis of Diaryliodonium Triflates: Optimization, Scope and Limitations
Öppna denna publikation i ny flik eller fönster >>Efficient and General One-Pot Synthesis of Diaryliodonium Triflates: Optimization, Scope and Limitations
2007 (Engelska)Ingår i: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 349, nr 17-18, s. 2610-2618Artikel i tidskrift (Refereegranskat) 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.

Nyckelord
arenes, aromatic substitution, diaryliodonium salts, hypervalent compounds, iodine, oxidation
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-25300 (URN)10.1002/adsc.200700373 (DOI)000251737500011 ()
Forskningsfinansiär
Vetenskapsrådet, 621-2006-4027
Tillgänglig från: 2008-06-16 Skapad: 2008-06-16 Senast uppdaterad: 2022-02-25Bibliografiskt granskad
3. Efficient one-pot synthesis of bis(4-tert-butylphenyl)iodonium triflate
Öppna denna publikation i ny flik eller fönster >>Efficient one-pot synthesis of bis(4-tert-butylphenyl)iodonium triflate
2009 (Engelska)Ingår i: Organic Syntheses, ISSN 0078-6209, E-ISSN 2333-3553, Vol. 86, s. 308-314Artikel i tidskrift (Refereegranskat) Published
Nationell ämneskategori
Annan medicinsk grundvetenskap Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-29390 (URN)10.1002/0471264229.os086.29 (DOI)
Forskningsfinansiär
Vetenskapsrådet, 621-2006-4027
Anmärkning

Published on the Web 6/16/2009

Tillgänglig från: 2010-01-04 Skapad: 2009-08-26 Senast uppdaterad: 2023-07-28Bibliografiskt granskad
4. Regiospecific One-Pot Synthesis of Diaryliodonium Tetrafluoroborates from Arylboronic Acids and Aryl Iodides
Öppna denna publikation i ny flik eller fönster >>Regiospecific One-Pot Synthesis of Diaryliodonium Tetrafluoroborates from Arylboronic Acids and Aryl Iodides
2008 (Engelska)Ingår i: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 73, nr 12, s. 4602-4607Artikel i tidskrift (Refereegranskat) 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.

Nyckelord
diaryliodonium salts, MCPBA
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-25301 (URN)10.1021/jo8004974 (DOI)000256757100030 ()
Forskningsfinansiär
Vetenskapsrådet, 621-2006-4027
Tillgänglig från: 2008-06-16 Skapad: 2008-06-16 Senast uppdaterad: 2022-02-25Bibliografiskt granskad
5. α-Arylation by Rearrangement: On the Reaction of Enolates with Diaryliodonium Salts
Öppna denna publikation i ny flik eller fönster >>α-Arylation by Rearrangement: On the Reaction of Enolates with Diaryliodonium Salts
2010 (Engelska)Ingår i: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 16, nr 28, s. 8251-8254Artikel i tidskrift (Refereegranskat) 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).

Nyckelord
arylation, density functional calculations, hypervalent compounds, iodanes, reaction mechanisms
Nationell ämneskategori
Kemi Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-50196 (URN)10.1002/chem.201001110 (DOI)000280819100003 ()
Forskningsfinansiär
Vetenskapsrådet, 621-2008-3709Carl Tryggers stiftelse för vetenskaplig forskning , 08:288Carl Tryggers stiftelse för vetenskaplig forskning , 09:281Knut och Alice Wallenbergs Stiftelse
Anmärkning

authorCount :4

Tillgänglig från: 2010-12-21 Skapad: 2010-12-21 Senast uppdaterad: 2022-02-24Bibliografiskt granskad

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