Synthesis of two 8-[(anthraquinone-2-yl)-linked]-2'-deoxyadenosine 3'-benzyl hydrogen phosphates for studies of photoinduced hole transport in DNA

• Published in: Nucleosides, nucleotides & nucleic acids nucleotides & nucleic acids, 2005-01, Vol.24 (2), p.85-110
• Main Authors: Abou-Elkhair, Reham A I, Netzel, Thomas L
• Format: Article
• Language: English
• Subjects: Deoxyadenine Nucleotides - chemical synthesis; Deoxyadenine Nucleotides - chemistry; DNA - chemistry; Molecular Structure; Oxidants, Photochemical - chemical synthesis; Oxidants, Photochemical - chemistry
• ISSN: 1525-7770
• DOI: 10.1081/NCN-200051894

The challenge in working with anthraquinone-2'-deoxyadenosine (AQ-dA) conjugates is that they are insoluble in water and only sparingly soluble in most organic solvents. However, water-soluble AQ-dA conjugates with short linkers are required for study of their electrochemical and intramolecular electron transfer properties in this solvent prior to their use in laser kinetics investigations of photoinduced hole (cation) transport in DNA. This article first describes the synthesis of a water-soluble, ethynyl-linked AQ-dA conjugate, 8-[(anthraquinone-2-yl)ethynyl]-2'-deoxyadenosine 3'-benzyl hydrogen phosphate, based on initial formation of a 5'-O-(4,4'-dimethoxytrityl) (5'-O-DMTr) intermediate. Because intended H2 over Pd/C reduction of the ethynyl linker in 5'-O-DMTr-protected 2'-deoxyadenosines cleaves the DMTr protecting group and precipitates multiple side products, this work also describes the synthesis of an ethylenyl-linked AQ-dA conjugate, 8-[2-(anthraquinone-2-yl)ethyl]-2'-deoxyadenosine 3'-benzyl hydrogen phosphate, starting with a 5'-O-tert-butyldiphenylsilyl protecting group.