Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Hydrogenation, Transfer Hydrogenation and Hydrogen Transfer Reactions Catalyzed by Iridium Complexes
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Pher Andersson)ORCID iD: 0000-0002-6053-8828
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The work described in this thesis is focused on the development of new bidentate iridium complexes and their applications in the asymmetric reduction of olefins, ketones and imines. Three new types of iridium complexes were synthesized, which included pyridine derived chiral N,P-iridium complexes, achiral NHC complexes and chiral NHC-phosphine complexes. A study of their catalytic applications demonstrated a high efficiency of the N,P-iridium complexes for asymmetric hydrogenation of olefins, with good enantioselectivity. The carbene complexes were found to be very efficient hydrogen transfer mediators capable of abstracting hydrogen from alcohols and subsequently transfer it to other unsaturated bonds. This hydrogen transferring property of the carbene complexes was used in the development of C–C and C–N bond formation reactions via the hydrogen borrowing process. The complexes displayed high catalytic reactivity using 0.5–1.0 mol% of the catalyst and mild reaction conditions. Finally chiral carbene complexes were found to be activated by hydrogen gas. Their corresponding iridium hydride species were able to reduce ketones and imines with high efficiency and enantioselectivity without any additives, base or acid.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2015. , 69 p.
Keyword [en]
Iridium catalyst, carbene, N, P - ligand, asymmetric hydrogenation, transfer hydrogenation, hydrogen transfer reaction, alkylation, olefin, ketone, amide
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-119701ISBN: 978-91-7649-255-0 (print)OAI: oai:DiVA.org:su-119701DiVA: diva2:847914
Public defence
2015-09-30, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:15 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Submitted. Paper 6: Manuscript.

 

Available from: 2015-09-08 Created: 2015-08-21 Last updated: 2015-09-08Bibliographically approved
List of papers
1. Iridium Catalysts with Chiral Bicyclic Pyridine-Phosphane Ligands for the Asymmetric Hydrogenation of Olefins
Open this publication in new window or tab >>Iridium Catalysts with Chiral Bicyclic Pyridine-Phosphane Ligands for the Asymmetric Hydrogenation of Olefins
2014 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, Vol. 2014, no 1, 140-146 p.Article in journal (Refereed) Published
Abstract [en]

New bicyclic pyridine-phosphane ligands were prepared, and their iridium complexes were evaluated in asymmetric hydrogenation of trisubstituted olefins with non-coordinating and weakly coordinating substituents. The iridium catalysts showed high reactivity and enantioselectivity for both types of olefins.

Keyword
Iridium, N, P ligands, Homogeneous catalysis, Hydrogenation, Asymmetric catalysis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-99864 (URN)10.1002/ejoc.201301141 (DOI)000328631700016 ()
Funder
Swedish Research Council
Note

AuthorCount:4;

Available from: 2014-01-24 Created: 2014-01-20 Last updated: 2017-12-06Bibliographically approved
2. Highly Enantioselective Iridium Catalyzed Hydrogenation of α, β-Unsaturated Esters
Open this publication in new window or tab >>Highly Enantioselective Iridium Catalyzed Hydrogenation of α, β-Unsaturated Esters
2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 34, 10609-10616 p.Article in journal (Refereed) Published
Abstract [en]

α,β-Unsaturated esters have been employed as substrates in iridium-catalyzed asymmetric hydrogenation. Full conversions and good to excellent enantioselectivities (up to 99 % ee) were obtained for a broad range of substrates with both aromatic- and aliphatic substituents on the prochiral carbon. The hydrogenated products are highly useful as building blocks in the synthesis of a variety of natural products and pharmaceuticals.

Keyword
asymmetric catalysis, chirality, hydrogenation, iridium, α, β-unsaturated esters
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-119677 (URN)10.1002/chem.201200907 (DOI)
Available from: 2015-08-21 Created: 2015-08-21 Last updated: 2017-12-04Bibliographically approved
3. Chiral Hetero- and Carbocyclic Compounds from the Asymmetric Hydrogenation of Cyclic Alkenes
Open this publication in new window or tab >>Chiral Hetero- and Carbocyclic Compounds from the Asymmetric Hydrogenation of Cyclic Alkenes
Show others...
2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 21, 6507-6513 p.Article in journal (Refereed) Published
Abstract [en]

Several types of chiral hetero- and carbocyclic compounds have been synthesized by using the asymmetric hydrogenation of cyclic alkenes. N,P-Ligated iridium catalysts reduced six-membered cyclic alkenes with various substituents and heterofunctionality in good to excellent enantioselectivity, whereas the reduction of five-membered cyclic alkenes was generally less selective, giving modest enantiomeric excesses. The stereoselectivity of the hydrogenation depended more strongly on the substrate structure for the five- rather than the six-membered cyclic alkenes. The major enantiomer formed in the reduction of six-membered alkenes could be predicted from a selectivity model and isomeric alkenes had complementary enantioselectivity, giving opposite optical isomers upon hydrogenation. The utility of the reaction was demonstrated by using it as a key step in the preparation of chiral 1,3-cis-cyclohexane carboxylates.

Keyword
asymmetric synthesis, heterocyclic compounds, homogeneous catalysis, hydrogenation, iridium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-119678 (URN)10.1002/chem.201104073 (DOI)
Available from: 2015-08-21 Created: 2015-08-21 Last updated: 2017-12-04Bibliographically approved
4. 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, 3576-3579 p.Article 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.

Keyword
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: 2017-12-04Bibliographically approved
5. 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, 11529-11537 p.Article 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: 2017-12-04Bibliographically approved
6. 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: 2016-01-29Bibliographically approved

Open Access in DiVA

fulltext(2444 kB)260 downloads
File information
File name FULLTEXT02.pdfFile size 2444 kBChecksum SHA-512
7f76917dcb51b33640b011384172000efcb6444bbebae6ac2965324f379ecc54e0927f9062f5728c4d59855bbfd72db1e3e85dd4379cd6a3bf77b037bad154c0
Type fulltextMimetype application/pdf

Search in DiVA

By author/editor
Quan, Xu
By organisation
Department of Organic Chemistry
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 261 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 403 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf