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Deracemization of Functionalized Alcohols via Combined Ruthenium and Enzyme Catalysis
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Responsible organisation
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The major part of this thesis describes the synthesis of enantiopure alcohols and diols by combining ruthenium-catalyzed racemization or epimerization and lipase-catalyzed asymmetric transformations. A minor part of this thesis is focused on ruthenium-catalyzed redox reactions for transfer hydrogenation of 1,3-cycloalkanediketones.

Kinetic resolution of racemic γ-hydroxy acid derivatives was performed via Pseudomonas cepacia lipase (PS-C)-catalyzed transesterification. γ-Hydroxy esters and γ-hydroxy amides were studied showing in higher selec-tivity and yields for the γ-hydroxy amides. The enzyme PS-C tolerates both variation in the chain length and different functionalities giving good to high enantioselectivity. Combining enzymatic kinetic resolution with a ruthenium-catalyzed racemization led to a dynamic kinetic resolution (DKR). The use of 2,4-dimethyl-3-pentanol as a hydrogen source to suppress ketone formation in the dynamic kinetic resolution increased the yields of the acetate product. The synthetic utility of this procedure was illustrated by the practical synthesis of the γ-lactone (R)-5-methyltetrahydrofuran-2-one.

A distereoselective transformation of cis/trans-1,3-cyclohexandiol using Candida antarctica lipase B (CALB)-catalyzed transesterification was of interest. Desymmetrization of cis-1,3-cyclohexanediol to the (R-monoacetate was successfully accomplished. Enantiopure (R,R)-diacetate was obtained from the (R)-monoacetate in a DYKAT process at room tem-perature. Metal- and enzyme-catalyzed transformation of cis/trans-1,3-cyclohexanediol using PS-C, gives a high diastereoselectivity for cis-diacetate. The (S)-mono-acetate was obtained from cis-diacetate by CALB-catalyzed hydrolysis. In addition, it was shown, by the use of deuterium-labeling that intramolecular acyl migration does not occur in the transformation of cis-monoacetate to the cis-diacetate.

Ruthenium-catalyzed transfer hydrogenation of 1,3-cyclohexanedione under microwave heating was developed as an efficient and fast method for the preparation of 1,3-cycloalkandiols.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi , 2006. , 51 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-789ISBN: 91-7155-200-6 (print)OAI: oai:DiVA.org:su-789DiVA: diva2:199234
Public defence
2006-01-26, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 13:00
Opponent
Supervisors
Available from: 2006-01-04 Created: 2006-01-04 Last updated: 2012-06-26Bibliographically approved
List of papers
1. Dynamic Kinetic Resolution of γ-Hydroxy acid Derivatives
Open this publication in new window or tab >>Dynamic Kinetic Resolution of γ-Hydroxy acid Derivatives
2002 In: Tetrahedron Letters, ISSN 0040-4039, Vol. 43, no 16, 2983-2986 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25246 (URN)
Note
Part of urn:nbn:se:su:diva-789Available from: 2006-01-04 Created: 2006-01-04Bibliographically approved
2. 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: 2017-12-13Bibliographically approved
3. Enzymatic Resolution, Desymmetrization and Dynamic Kinetic Asym-metric Transformation of 1,3-Cycloalkanediols
Open this publication in new window or tab >>Enzymatic Resolution, Desymmetrization and Dynamic Kinetic Asym-metric Transformation of 1,3-Cycloalkanediols
2006 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 71, no 17, 6309-6316 p.Article in journal (Refereed) Published
Abstract [en]

An efficient desymmetrization of cis-1,3-cyclohexanediol to (1S,3R)-3-(acetoxy)-1-cyclohexanol ((R,S)-2a) was performed via Candida antarctica lipase B (CALB)-catalyzed transesterification, in high yield (up to 93%) and excellent enantioselectivity (ee's up to >99.5%). (R,R)-Diacetate ((R,R)-3a) was obtained in a DYKAT process at room temperature from (1S,3R)-3-acetoxy-1-cyclohexanol ((R,S)-2a), in a high trans/cis ratio (91:9) and in excellent enantioselectivity of >99%. Metal- and enzyme-catalyzed dynamic transformation of cis/trans-1,3-cyclohexanediol using PS-C gave a high diastereoselectivity for cis-diacetate (cis/trans = 97:3). The (1R,3S)-3-acetoxy-1-cyclohexanol (ent-(R,S)-2a) was obtained from cis-diacetate by CALB-catalyzed hydrolysis in an excellent yield (97%) and selectivity (>99% ee). By deuterium labeling it was shown that intramolecular acyl migration does not occur in the transformation of cis-monoacetate to the cis-diacetate.

Place, publisher, year, edition, pages
American Chemical Society, 2006
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-25248 (URN)10.1021/jo060002n (DOI)
Note
Part of urn:nbn:se:su:diva-789Available from: 2006-01-04 Created: 2006-01-04 Last updated: 2017-12-13Bibliographically approved
4. Highly Efficient Ru-catalyzed Transfer Hydrogenation/Hydrogenation Procedure for 1,3-Cycloalkandiols using Controlled Microwave Heating
Open this publication in new window or tab >>Highly Efficient Ru-catalyzed Transfer Hydrogenation/Hydrogenation Procedure for 1,3-Cycloalkandiols using Controlled Microwave Heating
Manuscript (Other academic)
Identifiers
urn:nbn:se:su:diva-25249 (URN)
Note
Part of urn:nbn:se:su:diva-789Available from: 2006-01-04 Created: 2006-01-04 Last updated: 2010-01-13Bibliographically approved

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