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High Enantioselectivity of Chiral Sulfones byIridium Catalyzed Asymmetric Hydrogenation: An Efficient Access for Total Synthesis of Imperanene
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.
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.
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-182643OAI: oai:DiVA.org:uu-182643DiVA: diva2:560431
Available from: 2012-10-14 Created: 2012-10-14 Last updated: 2012-11-12
In thesis
1. Asymmetric Hydrogenation of Functionalized Olefins Using N,P-Ligated Iridium Complexes
Open this publication in new window or tab >>Asymmetric Hydrogenation of Functionalized Olefins Using N,P-Ligated Iridium Complexes
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Transition-metal-catalyzed asymmetric hydrogenation is one of the most efficient, straightforward, and well-established methods for preparing enantiomerically enriched compounds. Over the past decades, significant progress has been made with iridium, rhodium and ruthenium complexes to asymmetric hydrogenate a selection of olefins, such as, α,β-unsaturated carboxylic acid derivatives, ketones, imines and phosphonates. Although these metals have been applied successfully in the hydrogenation of olefins, they differ in their substrate tolerance.  Ruthenium and rhodium based catalysts require a coordinating group in the vicinity of the C=C bond. However, iridium based catalysts do not require this coordinating group, hence, asymmetric hydrogenation with iridium catalysts has been widely used for both functionalized and unfunctionalized olefin substrates. This thesis focuses on expanding the substrate scope for asymmetric hydrogenation using chiral N,P-ligated iridium catalysts. Papers I and II investigate the asymmetric hydrogenation of prochiral N-heterocyclic compounds prepared by ring-closing metathesis using the iridium catalysts developed in our group.  These substrates are interesting as they bear resemblance to pharmaceutically active compounds and therefore have tremendous value in medicinal chemistry.  Excellent enantioselectivities, up to >99% ee and conversions were obtained. In papers III and IV we synthesized many unsaturated acyclic and cyclic sulfones with varying substitution patterns.  The sulfones were subjected to hydrogenation using our N,P-ligated iridium catalysts, producing the chiral sulfone products in high enantiomeric excess (up to 99% ee). This methodology was combined with the Ramberg-Bäcklund reaction, offering a novel route to chiral allylic and homoallylic compounds. In addition to obtaining these chiral compounds in good yields, no decrease in enantiomeric excess was observed after the Ramberg-Bäcklund reaction. This strategy has been applied in the preparation of the chiral building block for renin inhibitors.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2012. 59 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 983
Keyword
asymmetric hydrogenation, iridium, Ramberg-Bäcklund reaction, sulfone, heterocycle, preclamol, remikiren
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-182648 (URN)978-91-554-8503-0 (ISBN)
Public defence
2012-11-29, A1:107A, BMC, Husargatan 3, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2012-11-07 Created: 2012-10-14 Last updated: 2013-01-23

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