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Dynamic Kinetic Asymmetric Transformation of 1,4-diols and Preparation of Trans-2,5-Disubstituted pyrrolidines
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2009 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, 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.

Place, publisher, year, edition, pages
2009. Vol. 50, no 26, 3237-3240 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-25588DOI: 10.1016/j.tetlet.2009.02.079ISI: 000267070700029OAI: oai:DiVA.org:su-25588DiVA: diva2:200015
Available from: 2008-11-20 Created: 2008-11-04 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Enantioselective Synthesis of Sec-Alcohol Derivatives and Diols via Combined Ruthenium and Enzyme Catalysis
Open this publication in new window or tab >>Enantioselective Synthesis of Sec-Alcohol Derivatives and Diols via Combined Ruthenium and Enzyme Catalysis
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The first part of this thesis describes the synthesis of enantiopure secondary alcohol derivatives. These syntheses are carried out via the combination of an enzyme as a resolution catalyst and a ruthenium catalyst as a racemization catalyst, in what is called dynamic kinetic resolution (DKR). By varying the resolution catalyst enantio-complementary processes can be obtained. A lipase (PS-C II) catalyzed DKR of γ-hydroxyamides gave the corresponding (R)-acetates in high yields and with high enantioselectivity. The synthetic usefulness of these obtained (R)-acetates was demonstrated by the synthesis of (R)-5-methyltetrahydrofurane-2-one. A protease (Subtilisin Carlsberg) catalyzed DKR of various secondary alcohols gave the corresponding (S)-acetates in high yields and with high enantioselectivity. In the second part of this thesis the DKR process has been extended into a dynamic kinetic asymmetric transformation (DYKAT) of diols. Various 1,5- and 1,4-diols were transformed into enantiopure diacetates in a lipase (CALB and PS-C II) catalyzed DYKAT. The synthetic utility of the obtained enantiopure diacetates were demonstrated by the synthesis of various enantiopure disubstituted heterocycles.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2008
Keyword
catalysis, kinetic resolution, ruthenium catalyst, Dynamic kinetic resolution, Dynamic Kinetic Asymmetric Transformation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-8298 (URN)978-91-7155-778-0 (ISBN)
Public defence
2008-12-12, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00
Opponent
Supervisors
Available from: 2008-11-20 Created: 2008-11-04 Last updated: 2012-06-26Bibliographically approved
2. Synthesis and asymmetric transformations of diols by enzyme- and ruthenium catalysis
Open this publication in new window or tab >>Synthesis and asymmetric transformations of diols by enzyme- and ruthenium catalysis
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
dynamic kinetic asymmetric transformation, diols, enzymatic transformations, catalysis, ruthenium, transfer hydrogenation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-8294 (URN)978-91-7155-769-8 (ISBN)
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

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