A synthetic approach to produce lysergic acid by virtue of an asymmetric ring opening (ARO) of symmetrical 3,6-disubstituted-7,10-hydroxymethyl bridgehead substituted oxabicycles is described. The use of a Rhodium(I)/JosiPhos(R,S) catalyst system to effect an ARO using an amine nucleophile furnishes an enantiopure tetrahydronapthalene intermediate with the amine conveniently installed at the 6 position as in lysergic acid, with appropriate stereochemistry; further which, two subsequent annulations are necessary to form the fused 3,5-substituted indole and tetrahydropyridine to complete the synthesis. Progress of this work is described herein along with future directions. The second chapter in this thesis describes the modular and stereoselective synthesis of tetrasubstituted helical alkenes via a palladium-catalyzed domino reaction under Catellani conditions. These helical alkenes possess potentially interesting photochemical properties as molecular motors / switches, and can be applicable in the materials sciences as molecular machines.
| Identifer | oai:union.ndltd.org:TORONTO/oai:tspace.library.utoronto.ca:1807/33407 |
| Date | 22 November 2012 |
| Creators | El-Salfiti, Mohamed Kamal |
| Contributors | Lautens, Mark |
| Source Sets | University of Toronto |
| Language | en_ca |
| Detected Language | English |
| Type | Thesis |
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