Synthesis and asymmetric transformations of diols by enzyme- and ruthenium catalysis
Stockholm University, Faculty of Science, Department of Organic Chemistry2008 (English)Doctoral thesis, comprehensive summary (Other academic)
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.
Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi , 2008. , 49 p.
dynamic kinetic asymmetric transformation, diols, enzymatic transformations, catalysis, ruthenium, transfer hydrogenation
Research subject Organic Chemistry
IdentifiersURN: urn:nbn:se:su:diva-8294ISBN: 978-91-7155-769-8OAI: oai:DiVA.org:su-8294DiVA: diva2:199998
2008-11-28, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Faber, Kurt, Professor
Bäckvall, Jan-Erling, Professor
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