Organocatalytic Approaches to Asymmetric Oxidation: Epoxidation of α-Branched Enals and α-Benzoyloxylation of Carbonyl Compounds

This work describes the development of enantioselective oxidation reactions of carbonyl compounds using covalent organocatalysis. In the first part, asymmetric epoxidation of α-branched α,β-unsaturated aldehydes with aqueous hydrogen peroxide is presented. An exceptionally synergistic combination of a primary cinchona alkaloid-derived amine and a chiral BINOL-derived phosphoric acid was found to promote the reaction with excellent enantiocontrol for a wide variety of α,β-disubstituted and α-monosubstituted enals. Conformational analysis of catalytically relevant intermediates using NMR and computational techniques enabled the rationalization of the absolute stereochemistry of products. The second part of this thesis describes a highly efficient direct catalytic asymmetric α-benzoyloxylation of cyclic ketones. The same primary amine paired with an inorganic acid was found to be an effective catalyst for a wide range of substrates. The methodology was applied to the first asymmetric synthesis of (+)-2β,4-dihydroxy-1,8-cineole, a predicted terpenoid metabolite in mammals. Preliminary investigations on the α-benzoyloxylation of α-branched aldehydes and α-branched enals using this catalytic system demonstrated significant potential of the method for the enantioselective formation of oxygenated quaternary stereocenters

Nucleophilic ring-opening of Methyl 1- Nitrocyclopropanecarboxylates

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

The Cinchona Primary Amine-Catalyzed Asymmetric Epoxidation and Hydroperoxidation of α,β-Unsaturated Carbonyl Compounds with Hydrogen Peroxide

Using cinchona alkaloid-derived primary amines as catalysts and aqueous hydrogen peroxide as the oxidant, we have developed highly enantioselective Weitz–Scheffer-type epoxidation and hydroperoxidation reactions of α,β-unsaturated carbonyl compounds (up to 99.5:0.5 er). In this article, we present our full studies on this family of reactions, employing acyclic enones, 5–15-membered cyclic enones, and α-branched enals as substrates. In addition to an expanded scope, synthetic applications of the products are presented. We also report detailed mechanistic investigations of the catalytic intermediates, structure–activity relationships of the cinchona amine catalyst, and rationalization of the absolute stereoselectivity by NMR spectroscopic studies and DFT calculations

Reactions of Donor-Acceptor Cyclopropanes with Naphthoquinones: Redox and Lewis Acid Catalysis Working in Concert

Reactions of 2-aryl cyclopropane dicarboxylates with naphthoquinones are reported. The key feature was the use of catalytic amounts of SnCl2, which acts as both electron donor and Lewis acid. By an in-situ umpolung of naphthoquinone the formerly electrophilic species is converted into a nucleophile that is able to trigger the ring-opening of the three-membered ring with formation of a new C-C bond. Treatment of these products with base under oxidative conditions resulted - by losing methyl formate - in cyclopentannulated products with fully conjugated π systems exhibiting intensive absorptions in the visible range

Improving disk read performance through block-level replication into free space

Disk performance for random access fares significantly worse compared to sequential access. Time required to transfer random blocks to or from disk is dominated by seeking and rotational delay. To improve the throughput and reduce the latency, one can apply techniques to increase the sequentiality of disk accesses, such as block rearrangement and replication. We introduce an approach to improve read performance by replicating blocks into file system free space at the block level. This makes the replication module independent of the file system and therefore easier to implement and verify. A solution that requires no changes to the file system is also easier to adopt. Supporting a new file system is a matter of writing a user-space component that understands its free block data structures. We implemented a prototype as a stacked device driver for Linux and evaluated its performance on a number of workloads.Science, Faculty ofComputer Science, Department ofGraduat