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Synthetic Transformations via Metal- and Enzyme-Catalyzed Dynamic Kinetic Resolution
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
2007 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: Institutionen för organisk kemi , 2007. , s. 66
Emneord [en]
ruthenium, racemization, lipase, dynamic kinetic resolution, secondary alcohol, Candida antarctica lipase B
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-6876ISBN: 978-91-7155-463-5 (tryckt)OAI: oai:DiVA.org:su-6876DiVA, id: diva2:197254
Disputas
2007-06-20, Magnélisalen, Arrheniuslaboratoriet, Svante Arrhenius väg 12, Stockholm, 10:00
Opponent
Veileder
Tilgjengelig fra: 2007-05-30 Laget: 2007-05-23 Sist oppdatert: 2017-10-16bibliografisk kontrollert
Delarbeid
1. New Efficient Ruthenium Catalysts for Racemization of Alcohols at Room Temperature
Åpne denne publikasjonen i ny fane eller vindu >>New Efficient Ruthenium Catalysts for Racemization of Alcohols at Room Temperature
2004 (engelsk)Inngår i: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 45, nr 36, s. 6799-6802Artikkel i tidsskrift (Fagfellevurdert) 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.

HSV kategori
Identifikatorer
urn:nbn:se:su:diva-24330 (URN)10.1016/j.tetlet.2004.07.013 (DOI)
Tilgjengelig fra: 2007-05-30 Laget: 2007-05-23 Sist oppdatert: 2017-12-13bibliografisk kontrollert
2. Highly compatible metal and enzyme catalysts for efficient dynamic kinetic resolution of alcohols at ambient temperature
Åpne denne publikasjonen i ny fane eller vindu >>Highly compatible metal and enzyme catalysts for efficient dynamic kinetic resolution of alcohols at ambient temperature
2004 Inngår i: Angewandte Chemie International Edition, ISSN 1433-7851, Vol. 43, nr 47, s. 6535-6539Artikkel i tidsskrift (Fagfellevurdert) Published
Identifikatorer
urn:nbn:se:su:diva-24331 (URN)
Merknad
Part of urn:nbn:se:su:diva-6876Tilgjengelig fra: 2007-05-30 Laget: 2007-05-23bibliografisk kontrollert
3. Combined Ruthenium(II) and Lipase Catalysis for Efficient Dynamic Kinetic Resolution of Secondary Alcohols. Insight into the Racemization Mechanism
Åpne denne publikasjonen i ny fane eller vindu >>Combined Ruthenium(II) and Lipase Catalysis for Efficient Dynamic Kinetic Resolution of Secondary Alcohols. Insight into the Racemization Mechanism
Vise andre…
2005 Inngår i: Journal of the American Chemical Society, ISSN 0002-7863, Vol. 127, nr 24, s. 8817-8825Artikkel i tidsskrift (Fagfellevurdert) Published
Identifikatorer
urn:nbn:se:su:diva-24332 (URN)
Merknad
Part of urn:nbn:se:su:diva-6876Tilgjengelig fra: 2007-05-30 Laget: 2007-05-23bibliografisk kontrollert
4. Highly Efficient Redox Isomerization of Allylic Alcohols at Ambient Temperature Catalyzed by Novel Ruthenium-Cyclopentadienyl Complexes–Insight into the Racemization Mechanism
Åpne denne publikasjonen i ny fane eller vindu >>Highly Efficient Redox Isomerization of Allylic Alcohols at Ambient Temperature Catalyzed by Novel Ruthenium-Cyclopentadienyl Complexes–Insight into the Racemization Mechanism
Vise andre…
2005 Inngår i: Chemistry : a European journal, ISSN 0947-6539, Vol. 11, nr 20, s. 5832-5842Artikkel i tidsskrift (Fagfellevurdert) Published
Identifikatorer
urn:nbn:se:su:diva-24333 (URN)
Merknad
Part of urn:nbn:se:su:diva-6876Tilgjengelig fra: 2007-05-30 Laget: 2007-05-23bibliografisk kontrollert
5. An enantioselective route to alpha-methyl carboxylic acids via metal and enzyme catalysis
Åpne denne publikasjonen i ny fane eller vindu >>An enantioselective route to alpha-methyl carboxylic acids via metal and enzyme catalysis
2007 (engelsk)Inngår i: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 9, nr 24, s. 5095-5098Artikkel i tidsskrift (Fagfellevurdert) 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.

HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-11741 (URN)10.1021/ol702261t (DOI)000250975000042 ()
Tilgjengelig fra: 2008-01-14 Laget: 2008-01-14 Sist oppdatert: 2017-10-16
6. Chemoenzymatic Dynamic Kinetic Resolution of Allylic Alcohols: A Highly Enantioselective Route to Acyloin Acetates
Åpne denne publikasjonen i ny fane eller vindu >>Chemoenzymatic Dynamic Kinetic Resolution of Allylic Alcohols: A Highly Enantioselective Route to Acyloin Acetates
2007 (engelsk)Inngår i: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 9, nr 17, s. 3401-3404Artikkel i tidsskrift (Fagfellevurdert) 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.

HSV kategori
Identifikatorer
urn:nbn:se:su:diva-24335 (URN)10.1021/ol071395v (DOI)000248658800052 ()
Tilgjengelig fra: 2007-05-30 Laget: 2007-05-23 Sist oppdatert: 2017-12-13bibliografisk kontrollert
7. High-yielding metalloenzymatic dynamic kinetic resolution of fluorinated aryl alcohols
Åpne denne publikasjonen i ny fane eller vindu >>High-yielding metalloenzymatic dynamic kinetic resolution of fluorinated aryl alcohols
2007 (engelsk)Inngår i: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 48, nr 31, s. 5471-5474Artikkel i tidsskrift (Fagfellevurdert) 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%).

HSV kategori
Identifikatorer
urn:nbn:se:su:diva-24336 (URN)10.1016/j.tetlet.2007.05.175 (DOI)000248527400026 ()
Tilgjengelig fra: 2007-05-30 Laget: 2007-05-23 Sist oppdatert: 2017-12-13bibliografisk kontrollert
8. Large Scale Metalloenzymatic Dynamic Kinetic Resolution of (rac)-1-Phenylethanol
Åpne denne publikasjonen i ny fane eller vindu >>Large Scale Metalloenzymatic Dynamic Kinetic Resolution of (rac)-1-Phenylethanol
Manuskript (Annet vitenskapelig)
Identifikatorer
urn:nbn:se:su:diva-24337 (URN)
Merknad
Part of urn:nbn:se:su:diva-6876Tilgjengelig fra: 2007-05-30 Laget: 2007-05-23 Sist oppdatert: 2010-01-13bibliografisk kontrollert
9. Divergent Asymmetric Synthesis of 3,5-Disubstituted Piperidines
Åpne denne publikasjonen i ny fane eller vindu >>Divergent Asymmetric Synthesis of 3,5-Disubstituted Piperidines
2006 (engelsk)Inngår i: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 71, nr 21, s. 8256-8260Artikkel i tidsskrift (Fagfellevurdert) Published
HSV kategori
Identifikatorer
urn:nbn:se:su:diva-24338 (URN)
Merknad

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Tilgjengelig fra: 2007-05-30 Laget: 2007-05-23 Sist oppdatert: 2017-12-13bibliografisk kontrollert

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