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Transition metal-catalysis: Applications of dynamic kinetic resolution in total synthesis and developments of novel methodologies using heterogeneous Pd catalysts
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2013 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

The first part of the thesis describes a general and efficient route for the enantioselective synthesis of various α-substituted ketones and their corresponding lactones. The two key steps in this synthesis are the ruthenium and CALB-catalyzed dynamic kinetic resolution (DKR) which provided the exocyclic acetates in high yields and excellent enantioselectivity and the subsequent Cu-catalyzed α-allylic substitution giving the corresponding α-substituted products with inversed stereochemistry in high yields. This synthetic route was applied to the synthesis of the naturally occurring (R)-10-methyl-6-undecanolide, via subsequent oxidative cleavage and Baeyer-Villiger oxidation.

In the second part, a new microwave-assisted methodology using a heterogeneous Pd nanocatalyst for Suzuki cross-couplings and hydrogenation of alkenes is presented. The catalytic system proved to be compatible with a wide range of functional groups and heteroatoms. In general, excellent yields were obtained within 45 min for the Suzuki cross-couplings and within 30 min for the hydrogenation reactions. The catalyst exhibited high recyclability with a low leaching in both cases.

A novel method to prepare γ-alkylidene lactones from alkynoic acids mediated by a heterogeneous Pd(II) catalyst is described in the last part of the thesis. The protocol proved to be highly stereo- and regioselective, affording the 5-exo-dig lactone as the single product in all cases. In general, internal alkynes were cyclized in high to excellent yields within 3 hours using 0.3 mol% of catalyst loading. For internal alkynes, the catalyst loading had to be increased to 0.5 mol% along with prolonged reaction times and elevated temperatures in order to obtained high yields. The catalyst showed some recyclability with low leaching.

Place, publisher, year, edition, pages
Stockholms universitets förlag, 2013. , 42 p.
National Category
Organic Chemistry
URN: urn:nbn:se:su:diva-89937OAI: diva2:621757
2013-06-05, Magnéli Hall, 14:00
Available from: 2013-05-20 Created: 2013-05-17 Last updated: 2013-05-20Bibliographically approved

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Nagendiran, Anuja
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Department of Organic Chemistry
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