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Studies of Hydrogenations and Isomerizations of Olefins and Alkylations of Amines Using Iridium Catalysts
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Syntetisk organisk kemi.
2012 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Uppsala: Acta Universitatis Upsaliensis, 2012. , s. 65
Serie
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 982
Nyckelord [en]
Iridium, Asymmetric, Hydrogenation, Isomerization, Alkylation
Nationell ämneskategori
Organisk kemi
Forskningsämne
Organisk kemi
Identifikatorer
URN: urn:nbn:se:uu:diva-182647ISBN: 978-91-554-8502-3 (tryckt)OAI: oai:DiVA.org:uu-182647DiVA, id: diva2:561044
Disputation
2012-11-28, B21, BMC, Husaragatan 3, Uppsala, 10:15 (Engelska)
Opponent
Handledare
Tillgänglig från: 2012-11-07 Skapad: 2012-10-14 Senast uppdaterad: 2013-01-23
Delarbeten
1. Bicyclic phosphine-thiazole ligands for the asymmetric hydrogenation of olefins
Öppna denna publikation i ny flik eller fönster >>Bicyclic phosphine-thiazole ligands for the asymmetric hydrogenation of olefins
2010 (Engelska)Ingår i: Tetrahedron: asymmetry, ISSN 0957-4166, E-ISSN 1362-511X, Vol. 21, nr 11-12, s. 1328-1333Artikel i tidskrift (Refereegranskat) 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.

Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:uu:diva-135190 (URN)10.1016/j.tetasy.2010.03.023 (DOI)000281095300002 ()
Tillgänglig från: 2010-12-06 Skapad: 2010-12-06 Senast uppdaterad: 2017-12-11Bibliografiskt granskad
2. Highly Flexible Synthesis of Chiral Azacycles via Iridium-Catalyzed Hydrogenation
Öppna denna publikation i ny flik eller fönster >>Highly Flexible Synthesis of Chiral Azacycles via Iridium-Catalyzed Hydrogenation
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2010 (Engelska)Ingår i: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 132, nr 26, s. 8880-8881Artikel i tidskrift (Refereegranskat) 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.

Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:uu:diva-135809 (URN)10.1021/ja103901e (DOI)000279561200033 ()20557052 (PubMedID)
Tillgänglig från: 2010-12-09 Skapad: 2010-12-08 Senast uppdaterad: 2017-12-11Bibliografiskt granskad
3. Chiral Hetero- and Carbocyclic Compounds from the Asymmetric Hydrogenation of Cyclic Alkenes
Öppna denna publikation i ny flik eller fönster >>Chiral Hetero- and Carbocyclic Compounds from the Asymmetric Hydrogenation of Cyclic Alkenes
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2012 (Engelska)Ingår i: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, nr 21, s. 6507-6513Artikel i tidskrift (Refereegranskat) 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.

Nyckelord
asymmetric synthesis, heterocyclic compounds, homogeneous catalysis, hydrogenation, iridium
Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:uu:diva-175620 (URN)10.1002/chem.201104073 (DOI)000304045000016 ()
Tillgänglig från: 2012-06-12 Skapad: 2012-06-11 Senast uppdaterad: 2017-12-07Bibliografiskt granskad
4. Highly Enantioselective Asymmetric Isomerization of Primary Allylic Alcohols with an Iridium-N,P Complex
Öppna denna publikation i ny flik eller fönster >>Highly Enantioselective Asymmetric Isomerization of Primary Allylic Alcohols with an Iridium-N,P Complex
2011 (Engelska)Ingår i: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 17, nr 40, s. 11143-11145Artikel i tidskrift (Refereegranskat) Published
Nyckelord
aldehydes, allylic alcohols, asymmetric catalysis, iridium, isomerization, N, P ligands
Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:uu:diva-164577 (URN)10.1002/chem.201101524 (DOI)000297013100011 ()
Tillgänglig från: 2011-12-21 Skapad: 2011-12-21 Senast uppdaterad: 2017-12-08Bibliografiskt granskad
5. Highly Enantioselective Iridium-Catalyzed Hydrogenation of α,β-Unsaturated Esters
Öppna denna publikation i ny flik eller fönster >>Highly Enantioselective Iridium-Catalyzed Hydrogenation of α,β-Unsaturated Esters
2012 (Engelska)Ingår i: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, nr 34, s. 10609-10616Artikel i tidskrift (Refereegranskat) 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.

Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:uu:diva-182641 (URN)10.1002/chem.201200907 (DOI)000307387300020 ()22807347 (PubMedID)
Tillgänglig från: 2012-10-14 Skapad: 2012-10-14 Senast uppdaterad: 2017-12-07Bibliografiskt granskad
6. Room Temperature and Solvent-Free Iridium-Catalyzed  Alkylation of Amines with Alcohols
Öppna denna publikation i ny flik eller fönster >>Room Temperature and Solvent-Free Iridium-Catalyzed  Alkylation of Amines with Alcohols
(Engelska)Manuskript (preprint) (Övrigt vetenskapligt)
Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:uu:diva-182645 (URN)
Tillgänglig från: 2012-10-16 Skapad: 2012-10-14 Senast uppdaterad: 2012-11-12

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