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Synthesis and asymmetric transformations of diols by enzyme- and ruthenium catalysis
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Responsible organisation
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The major part of this thesis describes the synthesis of aliphatic secondary diols and the development of lipase- and ruthenium-catalyzed asymmetric transformations of these diols.

Several acyclic 1,4-diols and 1,5-diols were synthesized, and by combining a lipase-catalyzed asymmetric transformation with a ruthenium-catalyzed epimerization, enantiomerically- and diastereomerically enriched diacetates were obtained. The scope and limitations of the system were also investigated, and some problems were encountered with electron-deficient diols. The diacetate products were further transformed into natural product heterocycles and chiral ligands.

A thorough study of the enzyme-catalyzed asymmetric transformation of 1,3-cyclohexanediol was also performed. It was found that there was a difference in the enzyme selectivity for the cis- and trans- diols, respectively, and while poor selectivity was observed for the trans-diol, cis-1,3-cyclohexanediol could be efficiently desymmetrized. By adding different epimerization catalysts, both cis- and trans-1,3-cyclohexanediol could be obtained in high enantio- and diastereoselectivities.

The use of hydrogen transfer for the reduction of cyclic 1,3-diketones was also demonstrated, and the reactions could in many cases be carried out in a microwave oven.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi , 2008. , 49 p.
Keyword [en]
dynamic kinetic asymmetric transformation, diols, enzymatic transformations, catalysis, ruthenium, transfer hydrogenation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-8294ISBN: 978-91-7155-769-8 (print)OAI: oai:DiVA.org:su-8294DiVA: diva2:199998
Public defence
2008-11-28, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Opponent
Supervisors
Available from: 2008-11-06 Created: 2008-10-28 Last updated: 2011-02-28Bibliographically approved
List of papers
1. Enantiopure 1,5-diols from dynamic kinetic asymmetric transformation: Useful synthetic intermediates for the preparation of heterocycles
Open this publication in new window or tab >>Enantiopure 1,5-diols from dynamic kinetic asymmetric transformation: Useful synthetic intermediates for the preparation of heterocycles
2008 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 10, no 10, 2027-2030 p.Article in journal (Refereed) Published
Abstract [en]

Dynamic kinetic asymmetric transformation (DYKAT) of a series of 1,5-diols has been performed in the presence of Candida antarctica lipase B (CALB), Pseudomonas cepacia lipase H (PS-C II), and ruthenium catalyst 4. The resulting optically pure 1,5-diacetates are useful synthetic intermediates, which was demonstrated by the syntheses of both an enantiopure 2,6-disubstituted piperidine and an enantiopure 3,5-disubstituted morpholine.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-25570 (URN)10.1021/ol800468h (DOI)000255694100038 ()
Available from: 2008-11-06 Created: 2008-10-28 Last updated: 2012-06-26Bibliographically approved
2. Enzyme- and ruthenium-catalyzed dynamic kinetic asymmetric transformation of 1,5-diols: Application to the synthesis of (+)-Solenopsin A
Open this publication in new window or tab >>Enzyme- and ruthenium-catalyzed dynamic kinetic asymmetric transformation of 1,5-diols: Application to the synthesis of (+)-Solenopsin A
2009 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 74, no 5, 1988-1993 p.Article in journal (Refereed) Published
Abstract [en]

Dynamic kinetic asymmetric transformation (DYKAT) of 1,5-diols via combined lipase and ruthenium catalysis provides enantiomerically pure diacetates in high diastereoselectivity, which can serve as intermediates in natural product synthesis. This is demonstrated by the synthesis of (+)-Solenopsin A.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-25571 (URN)10.1021/jo8025109 (DOI)000263921700022 ()
Available from: 2008-11-06 Created: 2008-10-28 Last updated: 2011-02-28Bibliographically approved
3. Dynamic Kinetic Asymmetric Transformation of 1,4-diols and Preparation of Trans-2,5-Disubstituted pyrrolidines
Open this publication in new window or tab >>Dynamic Kinetic Asymmetric Transformation of 1,4-diols and Preparation of Trans-2,5-Disubstituted pyrrolidines
2009 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1873-3581, Vol. 50, no 26, 3237-3240 p.Article in journal (Refereed) Published
Abstract [en]

Dynamic kinetic asymmetric transformation (DYKAT) of a series of 1,4-diols is carried out with Candida antarctica lipase B (CALB), Pseudomonas cepacia lipase II (PS-C II), and a ruthenium catalyst. A β-chloro-substituted 1,4-diol is successfully transformed into an optically pure 1,4-diacetate, which is a highly useful synthetic intermediate. The usefulness of the optically pure 1,4-diacetates is demonstrated by the synthesis of enantiopure 2,5-disubstituted pyrrolidines.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-25588 (URN)10.1016/j.tetlet.2009.02.079 (DOI)000267070700029 ()
Available from: 2008-11-20 Created: 2008-11-04 Last updated: 2011-03-01Bibliographically approved
4. Enzymatic resolution, desymmetrization and dynamic kinetic asymmetric transformation of 1,3-cycloalkanediols
Open this publication in new window or tab >>Enzymatic resolution, desymmetrization and dynamic kinetic asymmetric transformation of 1,3-cycloalkanediols
2006 In: Journal of organic chemistry, ISSN 0022-3263, Vol. 71, no 17, 6309-6316 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25573 (URN)
Note
Part of urn:nbn:se:su:diva-8294Available from: 2008-11-06 Created: 2008-10-28Bibliographically approved
5. Ruthenium-catalyzed transfer hydrogenation/hydrogenation of 1,3-cycloalkanediones to 1,3-cycloalkanediols using microwave heating
Open this publication in new window or tab >>Ruthenium-catalyzed transfer hydrogenation/hydrogenation of 1,3-cycloalkanediones to 1,3-cycloalkanediols using microwave heating
2006 In: Journal of organic chemistry, ISSN 0022-3263, Vol. 71, no 22, 8622-8625 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25574 (URN)
Note
Part of urn:nbn:se:su:diva-8294Available from: 2008-11-06 Created: 2008-10-28Bibliographically approved

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