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Transition Metal Catalysis for Selective Synthesis and Sustainable Chemistry
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry. (Pher G. Andersson)
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis discusses the preparation and use of transition-metal catalysts for selective organic chemical reactions. Specifically, two different matters have been studied; the asymmetric hydrogenation of carbon-carbon double bonds using N,P-ligated iridium catalysts and the metal-catalyzed transfer of small molecules from biomass to synthetic intermediates.

In the first part of this thesis, chiral N,P-ligands were synthesized and evaluated in iridium catalysts for the asymmetric hydrogenation of non- and weakly functionalized alkenes (Papers I & II). The new catalysts were prepared via chiral-pool strategies and exhibited superior properties for the reduction of certain types of alkenes. In particular, some of the catalysts showed excellent activity and selectivity in the enantioselective reduction of terminal alkenes, and the preparation of a modular catalyst library allowed the asymmetric hydrogenation of a wide range of 1,1-disubstituted alkenes with unprecedented efficiency and enantioselectivity (Paper III). Methods for the selective preparation of chiral hetero- and carbocyclic fragments using iridium-catalyzed asymmetric hydrogenation as an enantiodetermining key step were also developed. A range of elusive chiral building blocks that have applications in pharmaceutical and natural-product chemistry could thus be conveniently prepared (Papers IV & V).

The second part of this thesis deals with the catalytic decomposition of polysaccharides into sugar alcohols and the incorporation of their decomposition products into alkene substrates. Iridium-catalyzed dehydrogenative decarbonylation was found to decompose polyols into CO:H2 mixtures that could be used immediately in the ex situ low-pressure hydroformylation of styrene (Paper VI). The net process was thus the hydroformylation of alkenes with biomass-derived synthesis gas.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2012. , p. 125
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 984
Keyword [en]
Catalysis, Transition metals, Asymmetric catalysis, Hydrogenation, Sustainable chemistry
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-182900ISBN: 978-91-554-8507-8 (print)OAI: oai:DiVA.org:uu-182900DiVA, id: diva2:561345
Public defence
2012-11-30, B42, BMC, Husargatan 3, Uppsala, 10:00 (English)
Opponent
Supervisors
Available from: 2012-11-09 Created: 2012-10-18 Last updated: 2013-01-23
List of papers
1. Development of pinene-derived N,P ligands and their utility in catalytic asymmetric hydrogenation
Open this publication in new window or tab >>Development of pinene-derived N,P ligands and their utility in catalytic asymmetric hydrogenation
2007 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, no 47, p. 5603-5610Article in journal (Refereed) Published
Abstract [en]

New diastereomeric N,P-ligands, derived from the natural product (+)--pinene, have been synthesized and evaluated in iridium-catalyzed asymmetric hydrogenation. The ligands are tetrahydroquinoline derivatives synthesized directly from commercially available -pinene utilizing resolution or recrystallization to separate diastereomers. In reduction of a range of different trisubstituted alkenes the catalysts express very different activities ranging from no activity to high activity. One of the catalysts gives good ee values for some substrates.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-12344 (URN)10.1039/b713257n (DOI)000251269100016 ()
Available from: 2007-12-13 Created: 2007-12-13 Last updated: 2017-12-11Bibliographically approved
2. Biaryl phosphite-oxazolines from hydroxyl aminoacid derivatives: highly efficient modular ligands for Ir-catalyzed hydrogenation of alkenes
Open this publication in new window or tab >>Biaryl phosphite-oxazolines from hydroxyl aminoacid derivatives: highly efficient modular ligands for Ir-catalyzed hydrogenation of alkenes
Show others...
2008 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, no 33, p. 3888-3890Article in journal (Refereed) Published
Abstract [en]

High enantioselectivities and activities are achieved in the Ir-catalyzed hydrogenation of several unfunctionalized olefins using modular biaryl phosphite-oxazoline ligands from hydroxyl aminoacid derivatives, the presence of a biaryl phosphite group is crucial to this success.

Keyword
reduction, hydrogenation, diastereoselective syntheses, enantioselective syntheses (incl. cis/trans-isomerism), polyphenylalkane derivatives, carboxylic acid esters (benzene compounds), alcohols (benzene compounds)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-17849 (URN)10.1039/b806891g (DOI)000258686400015 ()
Available from: 2008-09-08 Created: 2008-09-08 Last updated: 2017-12-08Bibliographically approved
3. Iridium phosphite-oxazoline catalysts for the highly enantioselective hydrogenation of terminal alkenes
Open this publication in new window or tab >>Iridium phosphite-oxazoline catalysts for the highly enantioselective hydrogenation of terminal alkenes
Show others...
2009 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 131, no 34, p. 12344-12353Article in journal (Refereed) Published
Abstract [en]

A modular library of readily available phosphite-oxazoline ligands (L1-L16a-f) has been successfully applied for the first time in the Ir-catalyzed asymmetric hydrogenation of a broad range of highly unfunctionalized 1,1,-disubstituted terminal alkenes. Enantioselectivities up to >99% and full conversions were obtained in several 1,1-disubstituted alkenes, including substrate classes that have never been asymmetrically hydrogenated before (i.e., 1,1-heteoraryl-alkyl, 1,1-diaryl, trifluoromethyl, etc.). The results indicated that these catalytic systems have high tolerance to the steric and electronic requirements of the substrate and also to the presence of a neighboring polar group. The asymmetric hydrogenations were also performed using propylene carbonate as solvent, which allowed the Ir catalyst to be reused and maintained the excellent enantioselectivities.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-121863 (URN)10.1021/ja904152r (DOI)000269379600068 ()19658416 (PubMedID)
Available from: 2010-03-31 Created: 2010-03-31 Last updated: 2017-12-12Bibliographically approved
4. 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
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2010 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 132, no 26, p. 8880-8881Article 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
5. 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
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2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 21, p. 6507-6513Article 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
6. Selective, metal-catalyzed transfer of H2 and CO from polyols to alkenes
Open this publication in new window or tab >>Selective, metal-catalyzed transfer of H2 and CO from polyols to alkenes
2013 (English)In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 6, no 3, p. 426-429Article in journal (Refereed) Published
Keyword
catalysis, transition metals, renewable feedstocks
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-182817 (URN)10.1002/cssc.201200843 (DOI)000315715400008 ()
Available from: 2012-10-15 Created: 2012-10-15 Last updated: 2017-12-07Bibliographically approved

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