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NHC,P- and N,P-Iridium Catalysts for Hydrogenations and Hydrogen Transfer Reactions
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The work described in this thesis is focused on hydrogenation and hydrogen transfer reactions using iridium catalysts. The first part concerns the use of N-heterocyclic carbene-phosphine iridium complexes in alkylation reactions (Chapters 2 and 3) and the hydrogenation of ketones (Chapter 4). A number of N-heterocyclic carbene-phosphine iridium complexes have been prepared and evaluated as catalysts for C-N bond formation of amides using alcohols as the electrophile. This catalytic system can be used with a wide range of substrates at low catalyst loading (only 0.5 mol%) to furnish the desired products in up to 98% isolated yield. The achiral N-heterocyclic carbene-phosphine iridium complexes were also found to catalyze the methylation of ketones with methanol under mild conditions to afford the mono-methylated products in up to 98% isolated yield with low catalyst loading (1.0 mol%). Additionally, several chiral N-heterocyclic carbene-phosphine iridium complexes were synthesized and evaluated in asymmetric hydrogenation of ketones. The reactions were carried out at room temperature under base-free conditions to obtain the chiral alcohols in up to 96% ee in 30 minutes.

The second part of this thesis (Chapter 5) details the preparation of new N,P-iridium complexes which were found to be highly efficient catalysts for the asymmetric hydrogenation of challenging tetrasubstituted olefins. This catalytic system results in optically active compounds of high enantiomeric excess (up to 98% ee) as the single diasteroisomer.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2018.
Keywords [en]
Iridium catalyst, carbene, N, P-ligand, asymmetric hydrogenation, alkylation, hydrogen transfer reaction
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-152341ISBN: 978-91-7797-120-7 (print)ISBN: 978-91-7797-121-4 (print)OAI: oai:DiVA.org:su-152341DiVA, id: diva2:1179243
Public defence
2018-03-16, 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 3: Manuscript. Paper 4: Manuscript.

Available from: 2018-02-21 Created: 2018-01-31 Last updated: 2018-04-16Bibliographically approved
List of papers
1. C-N Coupling of Amides with Alcohols Catalyzed by N-Heterocyclic Carbene-Phosphine Iridium Complexes
Open this publication in new window or tab >>C-N Coupling of Amides with Alcohols Catalyzed by N-Heterocyclic Carbene-Phosphine Iridium Complexes
2015 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 80, no 22, p. 11529-11537Article in journal (Refereed) Published
Abstract [en]

N-heterocyclic carbene-phosphine iridium complexes (NHC-Ir) were developed/found to be a highly reactive catalyst for N-monoalkylation of amides with alcohols via hydrogen transfer. The reaction produced the desired product in high isolated yields using a wide range of substrates with low catalyst loading and short reaction times.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-119680 (URN)10.1021/acs.joc.5b01324 (DOI)000365462600033 ()
Funder
Swedish Research CouncilStiftelsen Olle Engkvist ByggmästareSwedish Energy AgencyKnut and Alice Wallenberg FoundationBerzelii Centre EXSELENT
Available from: 2015-08-21 Created: 2015-08-21 Last updated: 2018-03-21Bibliographically approved
2. C-C Coupling of Ketones with Methanol Catalyzed by a N-Heterocyclic Carbene-Phosphine Iridium Complex
Open this publication in new window or tab >>C-C Coupling of Ketones with Methanol Catalyzed by a N-Heterocyclic Carbene-Phosphine Iridium Complex
2015 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 21, p. 3576-3579Article in journal (Refereed) Published
Abstract [en]

An N-heterocyclic carbene–phosphine iridium complex system was found to be a very efficient catalyst for the methylation of ketone via a hydrogen transfer reaction. Mild conditions together with low catalyst loading (1 mol %) were used for a tandem process which involves the dehydrogenation of methanol, CC bond formation with a ketone, and hydrogenation of the new generated double bond by iridium hydride to give the alkylated product. Using this iridium catalyst system, a number of branched ketones were synthesized with good to excellent conversions and yields.

Keywords
C[BOND]C coupling reactions, hydrogen transfer, iridium, ketones, methylation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-119679 (URN)10.1002/chem.201405990 (DOI)000350116200013 ()
Funder
Swedish Research CouncilStiftelsen Olle Engkvist ByggmästareKnut and Alice Wallenberg Foundation
Available from: 2015-08-21 Created: 2015-08-21 Last updated: 2018-03-22Bibliographically approved
3. Highly Active Cationic NHC, Phosphine Iridium Catalysts for Base Free Asymmetric Hydrogenation of Ketones
Open this publication in new window or tab >>Highly Active Cationic NHC, Phosphine Iridium Catalysts for Base Free Asymmetric Hydrogenation of Ketones
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-119682 (URN)
Available from: 2015-08-21 Created: 2015-08-21 Last updated: 2018-02-06Bibliographically approved
4. Iridium-Catalyzed Enantio- and Diastereoselective Hydrogenation of Acyclic Tetra-Substituted Olefins
Open this publication in new window or tab >>Iridium-Catalyzed Enantio- and Diastereoselective Hydrogenation of Acyclic Tetra-Substituted Olefins
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-152346 (URN)
Available from: 2018-01-31 Created: 2018-01-31 Last updated: 2018-04-16Bibliographically approved

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