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Enantioselective Synthesis of Chiral Sulfones by Ir-Catalyzed Asymmetric Hydrogenation: A Facile Approach to the Preparation of Chiral Allylic and Homoallylic Compounds
Uppsala University, Sweden.
Uppsala University, Sweden.ORCID-id: 0000-0002-4465-6795
Uppsala University, Sweden.
University of KwaZulu-Natal, South Africa.
Vise andre og tillknytning
2012 (engelsk)Inngår i: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 134, nr 33, s. 13592-13595Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

A highly efficient and enantioselective Ir-catalyzed hydrogenation of unsaturated sulfones was developed. Chiral cyclic and acyclic sulfones were produced in excellent enantioselectivities (up to 98% ee). Coupled with the Ramberg–Bäcklund rearrangement, this reaction offers a novel route to chiral allylic and homoallylic compounds in excellent enantioselectivities (up to 97% ee) and high yields (up to 94%).

sted, utgiver, år, opplag, sider
2012. Vol. 134, nr 33, s. 13592-13595
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-120540DOI: 10.1021/ja306731uOAI: oai:DiVA.org:su-120540DiVA, id: diva2:853209
Tilgjengelig fra: 2015-09-11 Laget: 2015-09-11 Sist oppdatert: 2019-12-04bibliografisk kontrollert
Inngår i avhandling
1. Iridium Catalysed Asymmetric Hydrogenation of Olefins and Isomerisation of Allylic Alcohols
Åpne denne publikasjonen i ny fane eller vindu >>Iridium Catalysed Asymmetric Hydrogenation of Olefins and Isomerisation of Allylic Alcohols
2015 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: Department of Organic Chemistry, Stockholm University, 2015. s. 53
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-122419 (URN)978-91-76492-79-6 (ISBN)
Disputas
2015-12-18, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16B, Stockholm, 10:00 (engelsk)
Opponent
Veileder
Merknad

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.

Tilgjengelig fra: 2015-11-26 Laget: 2015-10-30 Sist oppdatert: 2015-11-25bibliografisk kontrollert

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