Walsh, Anthony (2015) Novel Methods to Access Bioactive Molecules. Doctoral thesis, University of Huddersfield.
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This thesis is divided into two chapters detailing research on applying microwave methodology to access aminated nucleosides in significantly reduced time frames, and applying the Belluš-Claisen reaction to produce non-proteogenic dipeptides.
1. Amination of Nucleosides Using Microwave Methodology
2,2’-Anhydrouridine undergoes a ring opening reaction with aliphatic amines to give the corresponding aminated product. Under conventional heating reaction times are extremely lengthy, taking at least 3 to 4 days and up to a month in the case of very hindered amines. A modified procedure using microwave irradiation has proven to drastically reduce reaction time and has allowed access to novel nucleosides on gram scale.
2. Functionalised Amino Acids via the Belluš-Claisen Rearrangement
The Belluš-Claisen reaction is a [3,3] sigmatropic rearrangement of allylic amines, ethers and thioethers to give the corresponding amide, ester of thioester. A modified procedure of the Belluš-Claisen rearrangement was used to prepare functionalised dipeptides by reaction of a ketene prepared from N-phthaloylglycyl chloride in situ with allylic amino acid derivatives in the presence of a Lewis Acid and diisopropylethylamine. Rearrangments were successfully carried out using N,N-diallyl alanine and N-allyl proline. A range of N-allyl proline derivatives are demonstrated. However, attempts to repeat the reaction with structurally more complex amino acids did not result in successful reactions.
|Item Type:||Thesis (Doctoral)|
|Subjects:||Q Science > QD Chemistry|
|Schools:||School of Applied Sciences|
|Depositing User:||Elizabeth Boulton|
|Date Deposited:||19 Jan 2016 15:26|
|Last Modified:||27 May 2016 00:48|
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