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Iridium-N,P-ligand-catalyzed enantioselective hydrogenation of diphenylvinylphosphine oxides and vinylphosphonates
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
2009 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 131, no 23, 8285-8289 p.Article in journal (Refereed) Published
Abstract [en]

Diphenylvinylphosphine oxides and di- and trisubstituted vinylphosphonates have been employed as substrates in iridium-catalyzed asymmetric hydrogenations. Complete conversions and excellent enantioselectivities (up to and above 99% ee) were observed for a range of substrates with both aromatic and aliphatic groups at the prochiral carbon. We have also hydrogenated electron-deficient carboxyethylvinylphosphonates with excellent stereoselectivity (up to and above 99% ee). The hydrogenated products of both classes of substrates are synthetically useful intermediates.

Place, publisher, year, edition, pages
2009. Vol. 131, no 23, 8285-8289 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-121865DOI: 10.1021/ja901437tISI: 000267623100057PubMedID: 19462955OAI: oai:DiVA.org:uu-121865DiVA: diva2:306891
Available from: 2010-03-31 Created: 2010-03-31 Last updated: 2014-01-21Bibliographically approved
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
2. Asymmetric Hydrogenations: Syntheses of Ligands and Expansion of Substrate Scope
Open this publication in new window or tab >>Asymmetric Hydrogenations: Syntheses of Ligands and Expansion of Substrate Scope
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Asymmetric hydrogenation has emerged as a versatile methodology to obtain a wide range of chiral precursors. This thesis focused on the synthesis of new chiral ligands and the expansion of the substrate scope of asymmetric hydrogenations. Paper I described the synthesis and evaluation of N,P-ligands for the Ir-catalyzed hydrogenations of unfunctionalized olefins. The substrate scope of Ir-catalyzed asymmetric hydrogenations is limited to a narrow range of “test” olefins. The foremost focus of this thesis was to expand the substrate scope of Ir-catalyzed asymmetric hydrogenations. Papers II and III disclosed the potential of the N,P-ligated Ir complexes in hydrogenation of the enol phosphinates. This substrate class is attractive because the hydrogenated products are chiral alkylphosphinates that can be transformed into chiral alcohols and chiral phosphines without sacrificing enantiopurity. A wide range of enol phosphinates were hydrogenated to excellent conversions and enatioselectivities. The hydrogenation of purely alkyl-substituted enol phosphinates in very high conversions and ee values was emphasized in these studies. Paper IV described the investigation of unfunctionalized enamines as substrates in Ir-catalyzed hydrogenation studies. The hydrogenation results and structural limitations of the substrates are presented. Paper V described the asymmetric hydrogenation of diphenylvinylphosphine oxides, di- and trisubstituted vinyl phosphonates. The hydrogenation of diphenylvinylphosphine oxides gives direct access to protected chiral phosphines. The hydrogenated products of vinylphosphonates are highly synthetically useful in pharmaceutical and material chemistry. Hydrogenation of E/Z mixtures of carboxyethyl vinylphosphonates with perfect enantioselectivities was striking in these studies. In paper VI, we have reported the development of a new, highly enantioselective synthetic route to building blocks with CF3 at the chiral center. Several functionalized and unfunctionalized CF3-substituted olefins were hydrogenated with varied degree of success. This methedilogy is useful in the formation of chiral fluorine-containing molecules for a wide range of applications. Paper VII described the hydrogenation of imines using the phosphine-free Cp*Ru/diamine complexes. Chiral version of this reaction was also examined. Despite the modest results, this is the first study to use phosphine-free Cp*Ru/diamine complexes as catalysts for the reduction of C=N double bonds.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2008. 67 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 569
Keyword
Catalysis, Asymmetric, Hydrogenations, Reductions, Olefins, Imines, Enol phosphinates, Transition metal, Complexes, Iridium, Enamines, Ruthenium, Ligands, Trifluoromethyl, Diphenylvinylphosphine oxides, Vinyl phosphonates
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-9353 (URN)978-91-554-7329-7 (ISBN)
Public defence
2008-12-02, B7:101a, BMC, Husargatan 3, Uppsala, 13:15
Opponent
Supervisors
Available from: 2008-11-11 Created: 2008-11-11 Last updated: 2014-01-21Bibliographically approved

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