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Highly Enantioselective Asymmetric Isomerization of Primary AllylicAlcohols with an Iridium–N,P Complex
Uppsala University, Sweden.
Uppsala University, Sweden.ORCID iD: 0000-0002-4465-6795
Uppsala University, Sweden; University of KwaZulu-Natal, South Africa.
2011 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 17, 11143-11145 p.Article in journal (Refereed) Published
Abstract [en]

Highly enantioselective asym. isomerization of a range of E- and Z- trisubstituted primary allylic alcs. to the corresponding chiral aldehydes catalyzed by a N,​P-​ligated iridium complex is reported.  Notably, the selectivity of this catalyst was less sensitive to steric effects in the asym. isomerization of Z-​trisubstituted allylic alcs. than E-​trisubstituted compds.

Place, publisher, year, edition, pages
2011. Vol. 17, 11143-11145 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-122304DOI: 10.1002/chem.201101524OAI: oai:DiVA.org:su-122304DiVA: diva2:865633
Available from: 2015-10-28 Created: 2015-10-28 Last updated: 2017-12-01Bibliographically approved
In thesis
1. Iridium Catalysed Asymmetric Hydrogenation of Olefins and Isomerisation of Allylic Alcohols
Open this publication in new window or tab >>Iridium Catalysed Asymmetric Hydrogenation of Olefins and Isomerisation of Allylic Alcohols
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The work described in this thesis is focused on exploring the efficacy of asymmetric iridium catalysis in the hydrogenation of challenging substrates, including precursors to chiral sulfones and chiral cyclohexanes. Furthermore, iridium catalysis was used to isomerise allylic alcohols to aldehydes, and in a formal total synthesis of Aliskiren (a renin inhibitor). A large variety of unsaturated sulfones (cyclic, acyclic, vinylic, allylic and homoallylic) were prepared and screened in the iridium catalysed hydrogenation reaction using a series of previously developed N,P-ligated Ir-catalysts. The outcome was a highly enantioselective (>90% ee) protocol to prepare sulfones bearing chiral carbon scaffolds, sometimes having purely aliphatic substituents at the stereogenic centre. Furthermore, performing the Ramberg-Bäcklund reaction on the chiral products, under optimised conditions, produced cyclic and acyclic unsaturated derivatives without erosion of enantiomeric excess. This hydrogenation protocol was also successful in the hydrogenation of a number of cyclohexene-containing compounds. Minimally functionalised, functionalised and heterocycle-containing cyclohexenes were hydrogenated in up to 99% ee. Hitherto, both chiral sulfones and chiral cyclohexanes have been challenging targets for most catalytic asymmetric methodologies. Although the preparation of aldehydes and ketones by isomerisation of the corresponding allylic alcohol is well established, there has been limited success in the development of good enantioselective protocols. For the isomerisation of a number γ,γ-allylic alcohols to the corresponding chiral aldehydes, high enantioselectivities (up to >99% ee) and modest yields were achieved using an N,P-iridium catalyst. Noteworthy is the high selectivity obtained for isomerisation of and dialkyl γ,γ-allylic alcohols, which prior to this study had been difficult to isomerise in high enantioselectivity. Preparation of a key intermediate used in the synthesis of Aliskiren, a renin inhibitor drug was also accomplished. Using a convergent synthesis strategy, two allylic alcohol fragments were hydrogenated with high enantiomeric excess (>92% ee). These fragments were then joined using a Julia-Kocienski reaction, providing >95% geometry around the C=C bond, which was crucial for the subsequent steps in the synthesis.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2015. 53 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-122419 (URN)978-91-76492-79-6 (ISBN)
Public defence
2015-12-18, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.

Available from: 2015-11-26 Created: 2015-10-30 Last updated: 2015-11-25Bibliographically approved

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