Site-specific deuteration of essential fatty acids towards the fight against ageing

• Main Author: Smarun, Alexey Vladimirovich
• Other Authors: School of Physical and Mathematical Sciences
• Format: Theses and Dissertations
• Language: English
• Published: 2016
• Subjects: DRNTU::Science
• Online Access: http://hdl.handle.net/10356/65979
• Institution: Nanyang Technological University

The aim of this dissertation was to investigate non-catalytic and catalytic synthetic routes for crucial ROS-resistant deuterium labelled essential polyunsaturated fatty acids (PUFAs). In order to perform selective catalytic H/D exchange of the bis-allylic position in methyl linoleate, a new complete series of cyclopentadienyl ruthenium complexes [(η5-C5MenH5-n)Ru(κ2-P,N-tBu2PIm)(CH3CN-κN)]PF6 has been successfully developed. In accordance to our initial proposal, structural modifications in these complexes did restrict the most deleterious isomerization pathway that previously resulted in conjugation of double bonds in methyl linoleate. Additionally, we conducted a series of kinetic and mechanistic studies of isomerization and deuteration reactions catalyzed by these complexes using simple terminal olefin as a substrate. These studies contrasted the influence of steric hindrance degree in their structure on their activity towards alkene isomerization. Finally, these complexes have been characterized by means of 1H, 13C and 31P NMR spectroscopy, mass spectroscopy and single crystal X-Ray analysis that provided evidence towards structural changes arisen from increased steric hindrance of cyclopentadienyl moiety.