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Studies of Hydrogenations and Isomerizations of Olefins and Alkylations of Amines Using Iridium Catalysts
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes three types of reactions that were carried out using iridium catalysts.

The first type is the iridium-catalyzed asymmetric hydrogenation of olefins. In paper I, the preparation of a new type of bicyclic thiazole-phosphine based iridium complex was described. The new catalysts have displayed high activity and enantioselectivity in the asymmetric hydrogenation of unfunctionalized olefins. Papers II and III focus on the expansion of the substrate scope for the iridium catalyzed asymmetric hydrogenation in which a number of heterocyclic olefins were evaluated. In paper IV, the enantioselective asymmetric hydrogenation of α, β-unsaturated esters was described. The chiral products bearing tertiary stereogenic centers obtained by hydrogenation have great synthetic value and have been used in the synthesis of pharmaceuticals as well as in the total synthesis of natural products.

The second type is the asymmetric isomerization of allylic alcohols. In paper V, both cis and trans primary allylic alcohols were isomerized to the corresponding β-chiral aldehydes in high enantioselectivities by an N,P-chelating iridium complex.

The third type is the selective mono-N-alkylation of amines with alcohols. In paper VI, a phosphine/NHC based iridium catalyst was synthesized and applied in the alkylation of amines. It is the first time that this type of transformation is carried out at room temperature.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2012. , 65 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 982
Keyword [en]
Iridium, Asymmetric, Hydrogenation, Isomerization, Alkylation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-182647ISBN: 978-91-554-8502-3 (print)OAI: oai:DiVA.org:uu-182647DiVA: diva2:561044
Public defence
2012-11-28, B21, BMC, Husaragatan 3, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2012-11-07 Created: 2012-10-14 Last updated: 2013-01-23
List of papers
1. Bicyclic phosphine-thiazole ligands for the asymmetric hydrogenation of olefins
Open this publication in new window or tab >>Bicyclic phosphine-thiazole ligands for the asymmetric hydrogenation of olefins
2010 (English)In: Tetrahedron: asymmetry, ISSN 0957-4166, E-ISSN 1362-511X, Vol. 21, no 11-12, 1328-1333 p.Article in journal (Refereed) Published
Abstract [en]

New bicyclic thiazole-based chiral N,P-chelating ligands were developed. High activities and enantioselectivities were achieved in the iridium-catalyzed asymmetric hydrogenation of olefins with the new ligands.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-135190 (URN)10.1016/j.tetasy.2010.03.023 (DOI)000281095300002 ()
Available from: 2010-12-06 Created: 2010-12-06 Last updated: 2017-12-11Bibliographically approved
2. Highly Flexible Synthesis of Chiral Azacycles via Iridium-Catalyzed Hydrogenation
Open this publication in new window or tab >>Highly Flexible Synthesis of Chiral Azacycles via Iridium-Catalyzed Hydrogenation
Show others...
2010 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 132, no 26, 8880-8881 p.Article in journal (Refereed) Published
Abstract [en]

A range of saturated chiral azacycles has been prepared in high yield and with high selectivity from simple starting materials. A modular approach with ring-closing metathesis as a key step was used to produce a number of five-, six-, and seven-membered cyclic alkenes. Asymmetric hydrogenation catalyzed by N,P-ligated iridium complexes gave saturated azacycles in high optical purity. This methodology was demonstrated in the synthesis of a pharmaceutical precursor.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-135809 (URN)10.1021/ja103901e (DOI)000279561200033 ()20557052 (PubMedID)
Available from: 2010-12-09 Created: 2010-12-08 Last updated: 2017-12-11Bibliographically 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
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-175620 (URN)10.1002/chem.201104073 (DOI)000304045000016 ()
Available from: 2012-06-12 Created: 2012-06-11 Last updated: 2017-12-07Bibliographically approved
4. Highly Enantioselective Asymmetric Isomerization of Primary Allylic Alcohols with an Iridium-N,P Complex
Open this publication in new window or tab >>Highly Enantioselective Asymmetric Isomerization of Primary Allylic Alcohols with an Iridium-N,P Complex
2011 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 17, no 40, 11143-11145 p.Article in journal (Refereed) Published
Keyword
aldehydes, allylic alcohols, asymmetric catalysis, iridium, isomerization, N, P ligands
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-164577 (URN)10.1002/chem.201101524 (DOI)000297013100011 ()
Available from: 2011-12-21 Created: 2011-12-21 Last updated: 2017-12-08Bibliographically approved
5. 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.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-182641 (URN)10.1002/chem.201200907 (DOI)000307387300020 ()22807347 (PubMedID)
Available from: 2012-10-14 Created: 2012-10-14 Last updated: 2017-12-07Bibliographically approved
6. Room Temperature and Solvent-Free Iridium-Catalyzed  Alkylation of Amines with Alcohols
Open this publication in new window or tab >>Room Temperature and Solvent-Free Iridium-Catalyzed  Alkylation of Amines with Alcohols
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-182645 (URN)
Available from: 2012-10-16 Created: 2012-10-14 Last updated: 2012-11-12

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