Enzyme- and Transition Metal-Catalyzed Asymmetric Transformations: Application of Enzymatic (D)KR in Enantioselective Synthesis

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Lihammar, Richard,1984-Stockholms universitet,Institutionen för organisk kemi (author)

Enzyme- and Transition Metal-Catalyzed Asymmetric Transformations : Application of Enzymatic (D)KR in Enantioselective Synthesis

BookEnglish2014

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Stockholm :Department of Organic Chemistry, Stockholm University,2014
78 s.
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LIBRIS-ID:oai:DiVA.org:su-108351
ISBN:9789176490082
https://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-108351URI

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Language:English
Summary in:English

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Subject category:vet swepub-contenttype
Subject category:dok swepub-publicationtype

Notes

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.
Dynamic kinetic resolution (DKR) is a powerful method for obtaining compounds with high optical purity. The process relies on the combination of a kinetic resolution with an in situ racemization. In this thesis, a combination of an immobilized hydrolase and a transition metal-based racemization catalyst was employed in DKR to transform racemic alcohols and amines into enantioenriched esters and amides, respectively.In the first part the DKR of 1,2-amino alcohols with different rings sizes and N-protecting groups is described. We showed that the immobilization method used to support the lipase strongly influenced the stereoselectivity of the reaction.The second part deals with the DKR of C3-functionalized cyclic allylic alcohols affording the corresponding allylic esters in high yields and high ee’s. The protocol was also extended to include carbohydrate derivatives, leading to inversion of a hydroxyl substituted chiral center on the carbohydrate.The third part focuses on an improved method for obtaining benzylic primary amines. By using a novel, recyclable catalyst composed of Pd nanoparticles on amino-functionalized mesocellular foam, DKR could be performed at 50 °C. Moreover, Lipase PS was for the first time employed in the DKR of amines.In the fourth part DKR was applied in the total synthesis of Duloxetine, a compound used in the treatment of major depressive disorder. By performing a six-step synthesis, utilizing DKR in the enantiodetermining step, Duloxetine could be isolated in an overall yield of 37% and an ee >96%.In the final part we investigated how the enantioselectivty of reactions catalyzed by Candida Antarctica lipase B for δ-substituted alkan-2-ols are influenced by water. The results showed that the enzyme displays much higher enantioselectivity in water than in anhydrous toluene. The effect was rationalized by the creation of a water mediated hydrogen bond in the active site that helps the enzyme form enantiodiscriminating binding modes.

Subject headings and genre

NATURVETENSKAP Kemi Organisk kemi hsv//swe
NATURAL SCIENCES Chemical Sciences Organic Chemistry hsv//eng
Dynamic Kinetic Resolution
Kinetic Resolution
Enzyme Catalysis
Asymmetric Synthesis
organisk kemi
Organic Chemistry

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Bäckvall, Jan-Erling,ProfessorStockholms universitet,Institutionen för organisk kemi (thesis advisor)
Kroutil, Wolfgang,ProfessorKarl Franzens Universität Graz, Austria (opponent)
Stockholms universitetInstitutionen för organisk kemi (creator_code:org_t)

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