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Enantioselective Synthesis of Sec-Alcohol Derivatives and Diols via Combined Ruthenium and Enzyme Catalysis
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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 [en]
catalysis, kinetic resolution, ruthenium catalyst, Dynamic kinetic resolution, Dynamic Kinetic Asymmetric Transformation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-8298ISBN: 978-91-7155-778-0 (print)OAI: oai:DiVA.org:su-8298DiVA: diva2:200016
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
List of papers
1. Kinetic Resolution and Chemoenzymatic Dynamic Kinetic Resolution of Functionalized γ-Hydroxy Amides
Open this publication in new window or tab >>Kinetic Resolution and Chemoenzymatic Dynamic Kinetic Resolution of Functionalized γ-Hydroxy Amides
2005 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 70, no 7, 2582-2587 p.Article in journal (Refereed) Published
Abstract [en]

An efficient kinetic resolution of racemic gamma-hydroxy amides 1 was performed via Pseudomas cepacia lipase (PS-C)-catalyzed transesterification. The enzyme PS-C tolerates both variation in the chain length and different functionalities giving good to high enantioselectivity (E values of up to > 250). The combination of enzymatic kinetic resolution with a ruthenium-catalyzed racemization led to a dynamic kinetic resolution. The use of 2,4-dimethyl-3-pentanol as a hydrogen source to suppress ketone formation in the dynamic kinetic resolution yields the corresponding acetates in good yield and good to high enantioselectivity (ee's up to 98%). The synthetic utility of this procedure was illustrated by the practical synthesis of the versatile intermediate gamma-lactone (R)-5-methyltetrahydrofuran-2-one.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-25584 (URN)10.1021/jo0478252 (DOI)000227928200020 ()
Available from: 2008-11-20 Created: 2008-11-04 Last updated: 2012-06-26Bibliographically approved
2. (S)-Selective Kinetic Resolution and Chemoenzymatic Dynamic Kinetic Resolution of Secondary Alcohols
Open this publication in new window or tab >>(S)-Selective Kinetic Resolution and Chemoenzymatic Dynamic Kinetic Resolution of Secondary Alcohols
Show others...
2006 In: Chemistry: a European Journal, ISSN 0947-6539, Vol. 12, no 1, 225-232 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25585 (URN)
Note
Part of urn:nbn:se:su:diva-8298Available from: 2008-11-20 Created: 2008-11-04Bibliographically approved
3. Enantiopure 1,5-diols from dynamic kinetic asymmetric transformation: Useful synthetic intermediates for the preparation of chiral 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 chiral heterocycles
2008 (English)Conference paper, Oral presentation with published abstract (Other academic)
Place, publisher, year, edition, pages
Washington, D.C.: American Chemical Society, 2008
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-27115 (URN)
Conference
235th ACS National Meeting, New Orleans, LA, United States, April 6-10, 2008
Available from: 2009-04-23 Created: 2009-04-23 Last updated: 2012-06-26Bibliographically approved
4. 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
5. 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

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