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Asymmetric Hydrogenations: Syntheses of Ligands and Expansion of Substrate Scope
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
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. , p. 67
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 569
Keywords [en]
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: urn:nbn:se:uu:diva-9353ISBN: 978-91-554-7329-7 (print)OAI: oai:DiVA.org:uu-9353DiVA, id: diva2:172774
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
List of papers
1. Development of new thiazole-based iridium catalysts and their applications in the asymmetric hydrogenation of trisubstituted olefins
Open this publication in new window or tab >>Development of new thiazole-based iridium catalysts and their applications in the asymmetric hydrogenation of trisubstituted olefins
2008 (English)In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 6, no 2, p. 366-373Article in journal (Refereed) Published
Abstract [en]

New thiazole-based chiral N,P-ligands that are open-chain analogues of known cyclic thiazole ligands have been synthesized and evaluated in the iridium-catalyzed asymmetric hydrogenation of trisubstituted olefins. Chirality was introduced into the ligands through a highly diastereoselective alkylation using Oppolzer's camphorsultam as chiral auxiliary. In general, the new catalysts are as reactive and selective as their cyclic counterparts for the asymmetric hydrogenation of various trisubstituted olefins.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-97720 (URN)10.1039/b714744a (DOI)000252106700020 ()
Available from: 2008-11-11 Created: 2008-11-11 Last updated: 2017-12-14Bibliographically approved
2. Asymmetric Hydrogenation of Enol Phosphinates by Iridium Catalysts Having N, P Ligands
Open this publication in new window or tab >>Asymmetric Hydrogenation of Enol Phosphinates by Iridium Catalysts Having N, P Ligands
2007 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 9, no 9, p. 1659-1661Article in journal (Refereed) Published
Abstract [en]

Enol phosphinates, which are structural analogues of enol acetates, have for the first time been employed as substrates for Ir-catalyzed asymmetric hydrogenation. A number of enol phosphinates have been synthesized and reduced successfully with up to and above 99% ee.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-97721 (URN)10.1021/ol070325l (DOI)
Available from: 2008-11-11 Created: 2008-11-11 Last updated: 2017-12-14Bibliographically approved
3. Asymmetric Hydrogenation of Di and Trisubstituted Enol Phosphinates with N,P-Ligated Iridium Complexes
Open this publication in new window or tab >>Asymmetric Hydrogenation of Di and Trisubstituted Enol Phosphinates with N,P-Ligated Iridium Complexes
2008 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 130, no 16, p. 5595-5599Article in journal (Refereed) Published
Abstract [en]

The iridium-catalyzed asymmetric hydrogenation of various di- and trisubstituted enol phosphinates has been studied. Excellent enantioselectivities (up to >99% ee) and full conversion were observed for a range of substrates with both aromatic and aliphatic side chains. Enol phosphinates are structural analogues of enol acetates, and the hydrogenated alkyl phosphinate products can easily be transformed into the corresponding alcohols with conservation of stereochemistry. We have also hydrogenated, in excellent ee, several purely alkyl-substituted enol phosphinates, producing chiral alcohols that are difficult to obtain highly enantioselectively from ketone hydrogenations.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-97722 (URN)10.1021/ja711372c (DOI)000255041400050 ()
Available from: 2008-11-11 Created: 2008-11-11 Last updated: 2017-12-14Bibliographically approved
4. Access to Chiral Tertiary Amines via Iridium Catalyzed Asymmetric Hydrogenation Of Enamines
Open this publication in new window or tab >>Access to Chiral Tertiary Amines via Iridium Catalyzed Asymmetric Hydrogenation Of Enamines
Show others...
2008 (English)In: Tetrahedron Letters, Vol. 49, no 51, p. 7290-7293Article in journal (Refereed) Published
Abstract [en]

The asymmetric hydrogenation of N,N-dialkyl and N-alkyl-N-aryl enaminesto chiral tertiary amines was studied. All the N,P-ligated iridium complexes investigated were active catalysts for the reaction, but only those with bicycle-supported oxazoline-phosphine ligands gave reasonable stereoinduction. The best catalyst produced a range of chiral tertiary amines in up to 87% ee.

National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-97723 (URN)10.1016/j.tetlet.2008.10.035 (DOI)000261532000015 ()
Available from: 2008-11-11 Created: 2008-11-11 Last updated: 2013-03-01Bibliographically approved
5. Iridium-N,P-ligand-catalyzed enantioselective hydrogenation of diphenylvinylphosphine oxides and vinylphosphonates
Open this publication in new window or tab >>Iridium-N,P-ligand-catalyzed enantioselective hydrogenation of diphenylvinylphosphine oxides and vinylphosphonates
2009 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 131, no 23, p. 8285-8289Article 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.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-121865 (URN)10.1021/ja901437t (DOI)000267623100057 ()19462955 (PubMedID)
Available from: 2010-03-31 Created: 2010-03-31 Last updated: 2017-12-12Bibliographically approved
6. Highly Selective Iridium-Catalyzed Asymmetric Hydrogenation of Trifluoromethyl Olefins: A New Route to Trifluoromethyl- Bearing Stereocenters
Open this publication in new window or tab >>Highly Selective Iridium-Catalyzed Asymmetric Hydrogenation of Trifluoromethyl Olefins: A New Route to Trifluoromethyl- Bearing Stereocenters
Show others...
2009 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 351, no 3, p. 375-378Article in journal (Refereed) Published
Abstract [en]

Fluorine-containing compounds are useful in many applications ranging from pharmaceuticals to ferroelectric crystals. We have developed a new, highly enantioselective synthetic route to trifluoromethyl-bearing stereocenters in up to 96% ee via asymmetric hydrogenation using N,P-ligated iridium catalysts. We also hydrogenated an isomeric mixture of olefins; this reaction gave the hydrogenation product highly enantioselectively (87% ee), and only the E isomer was present after the reaction had reached 56% conversion.

National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-97725 (URN)10.1002/adsc.200800645 (DOI)
Available from: 2008-11-11 Created: 2008-11-11 Last updated: 2017-12-14Bibliographically approved
7. Chemistry – An Asian Journal
Open this publication in new window or tab >>Chemistry – An Asian Journal
2008 In: Phosphine-Free RuCp*-Diamine Catalyzed Hydrogenation of Imi-nes, Vol. 3, p. 1390-1394Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-97726 (URN)
Available from: 2008-11-11 Created: 2008-11-11Bibliographically approved

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