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Bicyclic phosphine-thiazole ligands for the asymmetric hydrogenation of olefins
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för biokemi och organisk kemi.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för biokemi och organisk kemi.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för biokemi och organisk kemi.
2010 (engelsk)Inngår i: Tetrahedron: asymmetry, ISSN 0957-4166, E-ISSN 1362-511X, Vol. 21, nr 11-12, s. 1328-1333Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
2010. Vol. 21, nr 11-12, s. 1328-1333
HSV kategori
Identifikatorer
URN: urn:nbn:se:uu:diva-135190DOI: 10.1016/j.tetasy.2010.03.023ISI: 000281095300002OAI: oai:DiVA.org:uu-135190DiVA, id: diva2:374680
Tilgjengelig fra: 2010-12-06 Laget: 2010-12-06 Sist oppdatert: 2017-12-11bibliografisk kontrollert
Inngår i avhandling
1. Asymmetric Hydrogenations using N, P - Ligated Iridium Complexes
Åpne denne publikasjonen i ny fane eller vindu >>Asymmetric Hydrogenations using N, P - Ligated Iridium Complexes
2012 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
Abstract [en]

The research described in this thesis focuses on the catalytic asymmetric hydrogenation of prochiral olefins using N, P – chelated iridium catalysts. This catalytic system is tolerant to a wide range of substrates and performs better than the well-known ruthenium- and rhodium-catalytic systems for substrates devoid of coordinating groups in proximity of the olefin. Low catalytic loadings (often <1 %) and the high atom efficiency of this reaction make it a synthetically useful method of chiral molecule synthesis. The primary aim of this thesis was to develop new catalysts that rapidly and efficiently hydrogenate a broad range of alkenes asymmetrically. Papers I and II describe the synthesis and evaluation of new, highly efficient, chiral N, P – ligated iridium complexes. These catalysts were obtained in relatively few steps, while leaving open possibilities to modify and fine-tune their structure. Their versatility is ideally suited to both industrial uses and to equip any catalyst box. Paper III deals with a common problem of defluorination of vinylic fluorides during the hydrogenation. The catalyst designed in that work performs well for several substrates giving very low defluorination rates making it a good starting point for further improvements to cover a broader scope of vinyl fluorides. The structures of the catalysts from papers I and III also offers an easy approach to attach the catalyst ligands to a solid support. Paper IV explores hydrogenation of vinyl boronates, which gives synthetically interesting borane compounds with high enantioselectivities. Taking into account the rich chemistry of organic boranes, these compounds are very important. Paper V deals with hydrogenation of diphenylvinylphosphine oxides and vinyl phosphonates, another important classes of substrates that give chiral phosphorous containing compounds of interest in many fields of chemistry: such as medicinal chemistry and organocatalysis. In papers VI and VII we explore the Birch reaction as a source of prochiral olefins. By combining asymmetric hydrogenation with it, we obtain a powerful method to create chiral compounds with excellent enantioselectivities that are next to impossible to make by other routes. The products of the asymmetric hydrogenation are further modified by other well-known transformation to create other induced stereogenic centres.

sted, utgiver, år, opplag, sider
Uppsala: Acta Universitatis Upsaliensis, 2012. s. 61
Serie
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 939
Emneord
asymmetric hydrogenation, iridium, birch, boronates, fluorine
HSV kategori
Identifikatorer
urn:nbn:se:uu:diva-173459 (URN)978-91-554-8380-7 (ISBN)
Disputas
2012-06-08, B41, Husargatan 3, BMC, Uppsala, 10:15 (engelsk)
Opponent
Veileder
Tilgjengelig fra: 2012-05-15 Laget: 2012-04-24 Sist oppdatert: 2012-08-01bibliografisk kontrollert
2. Studies of Hydrogenations and Isomerizations of Olefins and Alkylations of Amines Using Iridium Catalysts
Åpne denne publikasjonen i ny fane eller vindu >>Studies of Hydrogenations and Isomerizations of Olefins and Alkylations of Amines Using Iridium Catalysts
2012 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
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
Emneord
Iridium, Asymmetric, Hydrogenation, Isomerization, Alkylation
HSV kategori
Forskningsprogram
Organisk kemi
Identifikatorer
urn:nbn:se:uu:diva-182647 (URN)978-91-554-8502-3 (ISBN)
Disputas
2012-11-28, B21, BMC, Husaragatan 3, Uppsala, 10:15 (engelsk)
Opponent
Veileder
Tilgjengelig fra: 2012-11-07 Laget: 2012-10-14 Sist oppdatert: 2013-01-23

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