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Dynamic Kinetic Asymmetric Transformation of 1,4-diols and Preparation of Trans-2,5-Disubstituted pyrrolidines
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
2009 (engelsk)Inngår i: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 50, nr 26, s. 3237-3240Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
2009. Vol. 50, nr 26, s. 3237-3240
HSV kategori
Identifikatorer
URN: urn:nbn:se:su:diva-25588DOI: 10.1016/j.tetlet.2009.02.079ISI: 000267070700029OAI: oai:DiVA.org:su-25588DiVA, id: diva2:200015
Tilgjengelig fra: 2008-11-20 Laget: 2008-11-04 Sist oppdatert: 2017-12-13bibliografisk kontrollert
Inngår i avhandling
1. Enantioselective Synthesis of Sec-Alcohol Derivatives and Diols via Combined Ruthenium and Enzyme Catalysis
Åpne denne publikasjonen i ny fane eller vindu >>Enantioselective Synthesis of Sec-Alcohol Derivatives and Diols via Combined Ruthenium and Enzyme Catalysis
2008 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: Institutionen för organisk kemi, 2008
Emneord
catalysis, kinetic resolution, ruthenium catalyst, Dynamic kinetic resolution, Dynamic Kinetic Asymmetric Transformation
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-8298 (URN)978-91-7155-778-0 (ISBN)
Disputas
2008-12-12, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00
Opponent
Veileder
Tilgjengelig fra: 2008-11-20 Laget: 2008-11-04 Sist oppdatert: 2012-06-26bibliografisk kontrollert
2. Synthesis and asymmetric transformations of diols by enzyme- and ruthenium catalysis
Åpne denne publikasjonen i ny fane eller vindu >>Synthesis and asymmetric transformations of diols by enzyme- and ruthenium catalysis
2008 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: Institutionen för organisk kemi, 2008. s. 49
Emneord
dynamic kinetic asymmetric transformation, diols, enzymatic transformations, catalysis, ruthenium, transfer hydrogenation
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-8294 (URN)978-91-7155-769-8 (ISBN)
Disputas
2008-11-28, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Opponent
Veileder
Tilgjengelig fra: 2008-11-06 Laget: 2008-10-28 Sist oppdatert: 2011-02-28bibliografisk kontrollert

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