uu.seUppsala University Publications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
The Birch reaction as a source of substrates for asymmetric hydrogenation
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
School of Chemistry, University of KwaZulu-Natal.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
(English)Manuscript (preprint) (Other academic)
Keyword [en]
birch reaction, asymmetric hydrogenation, cyclohexanes, 1, 6-diketone
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-173230OAI: oai:DiVA.org:uu-173230DiVA: diva2:517053
Available from: 2012-04-20 Created: 2012-04-20 Last updated: 2012-08-01
In thesis
1. Asymmetric Hydrogenations using N, P - Ligated Iridium Complexes
Open this publication in new window or tab >>Asymmetric Hydrogenations using N, P - Ligated Iridium Complexes
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
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.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2012. 61 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 939
Keyword
asymmetric hydrogenation, iridium, birch, boronates, fluorine
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-173459 (URN)978-91-554-8380-7 (ISBN)
Public defence
2012-06-08, B41, Husargatan 3, BMC, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2012-05-15 Created: 2012-04-24 Last updated: 2012-08-01Bibliographically approved

Open Access in DiVA

No full text

By organisation
Synthetical Organic Chemistry
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar

urn-nbn

Altmetric score

urn-nbn
Total: 403 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf