Design, Synthesis and Applications of Tyrosine-Derived Chiral Functionalised Polymers

This thesis documents the design and synthesis of chiral amino alcohol monomers 161, 162,167, chiral oxazolidine monomer 168 and chiral oxazolidinone monomers 203 and 204. The synthetic strategy relies on the key Suzuki coupling of aryl triflates derived from tyrosine with p-vinylphenylboronic acid where the resultant vinyl monomers are further modified to provide the desired functionality. / Me e e 161 Me2I'J OH 162 Me2N OH 167 H2N OH tDGh Me vie Me HN 0 HN 1° HN O 168 Mee 203 0 204 0 Model gel and macroporous-type suspension copolymerisations of styrene, divinylbenzene and vinylbenzyl chloride are investigated to allow modification of the experimental conditions to produce chloromethylpolystyrene beads 3 in optimum yield, size, shape and uniformity. Me jJ\m ©OGh> Me f We Me 3 217 H2N OH HN 1O 218 o The chiral amino alcohol 167 and oxazolidinone .204 monomers are subsequently polymerised utilising the previously optimised suspension protocol. Characterisation of the resultant gel-type polymers 217 and 218 confirms that the functionalised monomers are successfully incorporated with the desired loading. This versatile approach to the synthesis of chiral functionalised polymers ensures that only the chiral moiety is polymer-bound thus affording complete control. Finally, the utility of the polymer-bound amino alcohol 217 as a catalyst in the addition of dialkyizinc reagents to aldehydes and the application of the supported auxiliary 218 in asymmetric alkylation and aldol reactions are evaluated.