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The Birch reaction as a source of substrates for asymmetric hydrogenation
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Syntetisk organisk kemi.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Syntetisk organisk kemi.
School of Chemistry, University of KwaZulu-Natal.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Syntetisk organisk kemi.
(Engelska)Manuskript (preprint) (Övrigt vetenskapligt)
Nyckelord [en]
birch reaction, asymmetric hydrogenation, cyclohexanes, 1, 6-diketone
Nationell ämneskategori
Organisk kemi
Forskningsämne
Organisk kemi
Identifikatorer
URN: urn:nbn:se:uu:diva-173230OAI: oai:DiVA.org:uu-173230DiVA, id: diva2:517053
Tillgänglig från: 2012-04-20 Skapad: 2012-04-20 Senast uppdaterad: 2012-08-01
Ingår i avhandling
1. Asymmetric Hydrogenations using N, P - Ligated Iridium Complexes
Öppna denna publikation i ny flik eller fönster >>Asymmetric Hydrogenations using N, P - Ligated Iridium Complexes
2012 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
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
Nyckelord
asymmetric hydrogenation, iridium, birch, boronates, fluorine
Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:uu:diva-173459 (URN)978-91-554-8380-7 (ISBN)
Disputation
2012-06-08, B41, Husargatan 3, BMC, Uppsala, 10:15 (Engelska)
Opponent
Handledare
Tillgänglig från: 2012-05-15 Skapad: 2012-04-24 Senast uppdaterad: 2012-08-01Bibliografiskt granskad

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