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Development of New Efficient Iridium-Catalyzed Methods for the Construction of Carbon-Heteroatom Bonds
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0003-1331-9283
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Today’s society has a large demand for biologically active chemicals that can be used for example as pharmaceuticals and in the agriculture. These are normally constructed by assembling together several smaller chemical molecules. In order to achieve this, we need that these small molecules contain certain reactive sites, or in other words, that they are functionalized with certain atoms. The work in this thesis investigates and develops new methods to create functionalities in molecules, which in turn can be used to construct larger compounds and other materials important for our society.

 The methods herein developed are based on the use of metal catalysts to construct carbon-halogen bonds. Examples of halogens include bromide and iodide. When a molecule contains one (or more) of these bonds, it can be transformed in a simple chemical step into other compounds. The number of possible chemical transformations becomes almost endless. Thus, by accessing these compounds, chemical libraries can be created easily.

Throughout the work, sustainability has been prioritized by using, for the human health, friendly solvents whenever possible, by using versatile, stable and structurally simple but yet effective catalysts, and by minimizing the need to use unnecessary chemical activators.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2018.
Keywords [en]
Iridium Catalysis, Method development, Halogenation, Isomerization, C-H Activation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-161412ISBN: 978-91-7797-486-4 (print)ISBN: 978-91-7797-487-1 (electronic)OAI: oai:DiVA.org:su-161412DiVA, id: diva2:1258307
Public defence
2018-12-10, 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At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.

Available from: 2018-11-15 Created: 2018-10-24 Last updated: 2018-11-08Bibliographically approved
List of papers
1. Iridium-Catalyzed Isomerization/Bromination of Allylic Alcohols: Synthesis of alpha-Bromocarbonyl Compounds
Open this publication in new window or tab >>Iridium-Catalyzed Isomerization/Bromination of Allylic Alcohols: Synthesis of alpha-Bromocarbonyl Compounds
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2014 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 34, p. 10703-10709Article in journal (Refereed) Published
Abstract [en]

alpha-Brominated ketones and aldehydes, with two adjacent electrophilic carbon atoms, are highly valuable synthetic intermediates in organic synthesis, however, their synthesis from unsymmetrical ketones is very challenging, and current methods suffer from low selectivity. We present a new, reliable, and efficient method for the synthesis of alpha-bromocarbonyl compounds in excellent yields and with excellent selectivities. Starting from allylic alcohols as the carbonyl precursors, the combination of a 1,3-hydrogen shift catalyzed by iridium(III) with an electrophilic bromination gives alpha-bromoketones and aldehydes in good to excellent yields. The selectivity of the process is determined by the structure of the starting allylic alcohol; thus, alpha-bromoketones formally derived from unsymmetrical ketones can be synthesized in a straightforward and selective manner.

Keywords
allylic compounds, bromination, iridium, ketones, synthetic methods
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-107423 (URN)10.1002/chem.201402350 (DOI)000340505500019 ()
Funder
Knut and Alice Wallenberg FoundationSwedish Research CouncilVINNOVAWenner-Gren Foundations
Note

AuthorCount:5;

Available from: 2014-09-19 Created: 2014-09-15 Last updated: 2018-10-24Bibliographically approved
2. General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols: The Importance of the Halide Ligand
Open this publication in new window or tab >>General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols: The Importance of the Halide Ligand
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2016 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, no 44, p. 15659-15663Article in journal (Refereed) Published
Abstract [en]

Remarkably simple Ir-III catalysts enable the isomerization of primary and sec-allylic alcohols under very mild reaction conditions. X-ray absorption spectroscopy (XAS) and mass spectrometry (MS) studies indicate that the catalysts, with the general formula [Cp*Ir-III], require a halide ligand for catalytic activity, but no additives or additional ligands are needed.

Keywords
allylic alcohols, X-ray absorption spectroscopy, isomerization, iridium, reaction mechanisms
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-136049 (URN)10.1002/chem.201603825 (DOI)000386795700016 ()27650170 (PubMedID)
Funder
Knut and Alice Wallenberg FoundationSwedish Research CouncilVINNOVAWenner-Gren Foundations
Available from: 2016-12-21 Created: 2016-11-29 Last updated: 2018-11-12Bibliographically approved
3. Base- and Additive-Free Ir-Catalyzed ortho-Iodination of Benzoic Acids: Scope and Mechanistic Investigations
Open this publication in new window or tab >>Base- and Additive-Free Ir-Catalyzed ortho-Iodination of Benzoic Acids: Scope and Mechanistic Investigations
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2018 (English)In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 8, no 2, p. 920-925Article in journal (Refereed) Published
Abstract [en]

A protocol for the C-H activation/iodination of benzoic acids catalyzed by a simple iridium complex has been developed. The method described in this paper allows the ortho-selective iodination of a variety of benzoic acids under extraordinarily mild conditions in the absence of any additive or base in 1,1,1,3,3,3-hexafluoroisopropanol as the solvent. The iridium catalyst used tolerates air and moisture, and selectively gives ortho-iodobenzoic acids with high conversions. Mechanistic investigations revealed that an Ir(III)/Ir(V) catalytic cycle operates, and that the unique properties of HFIP enables the C-H iodination using the carboxylic moiety as a directing group.

Keywords
C-H iodination, benzoic acids, iridium catalysis, 1, 1, 1, 3, 3, 3-hexafluoroisopropanol, hydrogen bonding
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-153631 (URN)10.1021/acscatal.7b02987 (DOI)000424735000022 ()
Funder
Swedish Research CouncilSwedish Research Council FormasKnut and Alice Wallenberg Foundation
Available from: 2018-03-13 Created: 2018-03-13 Last updated: 2018-10-24Bibliographically approved
4. Selective C-H Iodination of Benzamides and Weinreb Amides through Iridium and Acid Catalysis
Open this publication in new window or tab >>Selective C-H Iodination of Benzamides and Weinreb Amides through Iridium and Acid Catalysis
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-161523 (URN)
Available from: 2018-11-01 Created: 2018-11-01 Last updated: 2018-11-02Bibliographically approved

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