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Synthetic Transformations via Metal- and Enzyme-Catalyzed Dynamic Kinetic Resolution
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with the preparation of a new half-sandwich type ruthenium(II)- catalyst for racemization of optically active secondary alcohols and the development of a highly efficient method in combination with lipases such as Candida antarctica lipase B and Pseudomonas cepacia lipase for dynamic kinetic resolution of various functionalized alcohols under mild reaction conditions.

It was shown that the RuCl(CO)25-C5Ph5) complex can racemize optically active aliphatic and aromatic secondary alcohols at room temperature in rather short times. Different parameters, such as the nature of the catalyst, catalyst loading and solvent effect were studied. After the optimization steps, the Ru-catalyzed racemization of (S)-1-phenylethanol in the presence of Candida antarctica lipase B was also investigated. The compatibility of the metal- and enzyme-catalyzed reactions led to a highly efficient coupled catalytic system for transformation of racemic alcohols to their enantiomerically pure acetates. This protocol was applied for a wide range of secondary alcohols. It was shown that in the case of allylic alcohols the obtained enantiopure allylic acetates are useful compounds for synthesis of α-methyl carboxylic acids such as (R)-Flurbiprofen and acyloin acetates. Highly selective dynamic kinetic asymmetric transformation of 3,5-piperidine diol to deliver various 3,5-dioxygenated piperidines is also described.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi , 2007. , 66 p.
Keyword [en]
ruthenium, racemization, lipase, dynamic kinetic resolution, secondary alcohol, Candida antarctica lipase B
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-6876ISBN: 978-91-7155-463-5 (print)OAI: oai:DiVA.org:su-6876DiVA: diva2:197254
Public defence
2007-06-20, Magnélisalen, Arrheniuslaboratoriet, Svante Arrhenius väg 12, Stockholm, 10:00
Opponent
Supervisors
Available from: 2007-05-30 Created: 2007-05-23 Last updated: 2017-10-16Bibliographically approved
List of papers
1. New Efficient Ruthenium Catalysts for Racemization of Alcohols at Room Temperature
Open this publication in new window or tab >>New Efficient Ruthenium Catalysts for Racemization of Alcohols at Room Temperature
2004 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 45, no 36, 6799-6802 p.Article in journal (Refereed) Published
Abstract [en]

5-Pentaphenylcyclopentadienyl)RuCl(CO)2 was found to catalyze efficiently the racemization of chiral alcohols such as (S)-1-phenylethanol, (S)-1-phenylpropan-2-ol, (S)-4-phenylbutan-2-ol and (S)-4-methoxy-1-phenylethanol at room temperature in the presence of a base. The catalytic activity of three other Ru(II) complexes was also investigated. The effects of halide and solvent were studied as well.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-24330 (URN)10.1016/j.tetlet.2004.07.013 (DOI)
Available from: 2007-05-30 Created: 2007-05-23 Last updated: 2017-12-13Bibliographically approved
2. Highly compatible metal and enzyme catalysts for efficient dynamic kinetic resolution of alcohols at ambient temperature
Open this publication in new window or tab >>Highly compatible metal and enzyme catalysts for efficient dynamic kinetic resolution of alcohols at ambient temperature
2004 In: Angewandte Chemie International Edition, ISSN 1433-7851, Vol. 43, no 47, 6535-6539 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24331 (URN)
Note
Part of urn:nbn:se:su:diva-6876Available from: 2007-05-30 Created: 2007-05-23Bibliographically approved
3. Combined Ruthenium(II) and Lipase Catalysis for Efficient Dynamic Kinetic Resolution of Secondary Alcohols. Insight into the Racemization Mechanism
Open this publication in new window or tab >>Combined Ruthenium(II) and Lipase Catalysis for Efficient Dynamic Kinetic Resolution of Secondary Alcohols. Insight into the Racemization Mechanism
Show others...
2005 In: Journal of the American Chemical Society, ISSN 0002-7863, Vol. 127, no 24, 8817-8825 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24332 (URN)
Note
Part of urn:nbn:se:su:diva-6876Available from: 2007-05-30 Created: 2007-05-23Bibliographically approved
4. Highly Efficient Redox Isomerization of Allylic Alcohols at Ambient Temperature Catalyzed by Novel Ruthenium-Cyclopentadienyl Complexes–Insight into the Racemization Mechanism
Open this publication in new window or tab >>Highly Efficient Redox Isomerization of Allylic Alcohols at Ambient Temperature Catalyzed by Novel Ruthenium-Cyclopentadienyl Complexes–Insight into the Racemization Mechanism
Show others...
2005 In: Chemistry : a European journal, ISSN 0947-6539, Vol. 11, no 20, 5832-5842 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24333 (URN)
Note
Part of urn:nbn:se:su:diva-6876Available from: 2007-05-30 Created: 2007-05-23Bibliographically approved
5. An enantioselective route to alpha-methyl carboxylic acids via metal and enzyme catalysis
Open this publication in new window or tab >>An enantioselective route to alpha-methyl carboxylic acids via metal and enzyme catalysis
2007 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 9, no 24, 5095-5098 p.Article in journal (Refereed) Published
Abstract [en]

Dynamic kinetic resolution of allylic alcohols to allylic acetates followed by copper-catalyzed allylic substitution gave alkenes in high yields and high optical purity. Subsequent oxidative C-C double bond cleavage afforded pharmaceutically important alpha-methyl substituted carboxylic acids in high ee.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-11741 (URN)10.1021/ol702261t (DOI)000250975000042 ()
Available from: 2008-01-14 Created: 2008-01-14 Last updated: 2017-10-16
6. Chemoenzymatic Dynamic Kinetic Resolution of Allylic Alcohols: A Highly Enantioselective Route to Acyloin Acetates
Open this publication in new window or tab >>Chemoenzymatic Dynamic Kinetic Resolution of Allylic Alcohols: A Highly Enantioselective Route to Acyloin Acetates
2007 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 9, no 17, 3401-3404 p.Article in journal (Refereed) Published
Abstract [en]

Dynamic kinetic resolution (DKR) of a series of sterically hindered allylic alcohols has been conducted with Candida antarctica lipase B (CALB) and ruthenium catalyst 1. The optically pure allylic acetates obtained were subjected to oxidative cleavage to give the corresponding acylated acyloins in high yields without loss of chiral information.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-24335 (URN)10.1021/ol071395v (DOI)000248658800052 ()
Available from: 2007-05-30 Created: 2007-05-23 Last updated: 2017-12-13Bibliographically approved
7. High-yielding metalloenzymatic dynamic kinetic resolution of fluorinated aryl alcohols
Open this publication in new window or tab >>High-yielding metalloenzymatic dynamic kinetic resolution of fluorinated aryl alcohols
2007 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 48, no 31, 5471-5474 p.Article in journal (Refereed) Published
Abstract [en]

Dynamic kinetic resolution (DKR) of various fluorinated aryl alcohols by a combination of lipase-catalyzed enzymatic resolution with in situ ruthenium-catalyzed alcohol racemization is described. (R)-Selective Candida antarctica lipase B (CALB) was employed for transesterification of different fluoroaryl alcohols in DKR reactions delivering the corresponding acetates in high yield (97%) with excellent enantiomeric excess (98%).

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-24336 (URN)10.1016/j.tetlet.2007.05.175 (DOI)000248527400026 ()
Available from: 2007-05-30 Created: 2007-05-23 Last updated: 2017-12-13Bibliographically approved
8. Large Scale Metalloenzymatic Dynamic Kinetic Resolution of (rac)-1-Phenylethanol
Open this publication in new window or tab >>Large Scale Metalloenzymatic Dynamic Kinetic Resolution of (rac)-1-Phenylethanol
Manuscript (Other academic)
Identifiers
urn:nbn:se:su:diva-24337 (URN)
Note
Part of urn:nbn:se:su:diva-6876Available from: 2007-05-30 Created: 2007-05-23 Last updated: 2010-01-13Bibliographically approved
9. Divergent Asymmetric Synthesis of 3,5-Disubstituted Piperidines
Open this publication in new window or tab >>Divergent Asymmetric Synthesis of 3,5-Disubstituted Piperidines
2006 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 71, no 21, 8256-8260 p.Article in journal (Refereed) Published
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-24338 (URN)
Note

Part of urn:nbn:se:su:diva-6876

Available from: 2007-05-30 Created: 2007-05-23 Last updated: 2017-12-13Bibliographically approved

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