Date of Award

2019

Document Type

Open Access Dissertation

Degree Name

Doctor of Philosophy in Chemistry (PhD)

Administrative Home Department

Department of Chemistry

Advisor 1

Shiyue Fang

Committee Member 1

Marina Tanasova

Committee Member 2

Tarun Dam

Committee Member 3

Feng Zhao

Abstract

Oligodeoxynucleotides (ODNs) containing electrophilic groups are useful in many studies including antisense drug development and DNA/protein interaction. Due to the use of strong nucleophiles for cleavage and deprotection, traditional ODN synthesis methods are not suitable for their preparation. To solve this problem, a new ODN synthesis technology using the 1,3- dithiane-2-yl-methoxycarbonyl (Dmoc) function as protecting groups and linker has been developed. Furthermore, Dmoc-derivatives were developed to demonstrate the feasibility of the technology. The Dmoc and Dmoc derivative functions are stable under all ODN synthesis conditions using the phosphoramidite chemistry. Upon oxidation of the sulfides in them, because of the drastically increased acidity of H-2, the groups and linker are readily cleaved under nearly non-nucleophilic conditions. Many sensitive electrophiles were able to be incorporated on DNA strands successfully using these technologies. These include but are not limited to sensitive thioester, ethyl ester, alkyl chloride, and α-chloroacetamide moieties.

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