Alkylation of Adenine with Functionalized tert.-Propargyl Carbonates. Synthesis of 3'-Hydroxymethyladenallene - a New Analogue of 2'-Deoxyadenosine

Article abstract of DOI:10.1016/0040-4020(94)00964-V

Esters 9d - 9g derived from acetylenic carbinol 5 were prepared and they were studied as potential alkylating agents with adenine (10), N⁶-benzoyl- and N⁶-dimethylamino-methyleneadenine (16 and 17).Carbonates 9f and 9g were the most suitable giving allene 11 and acetylene 12 (after N-deprotection in case of 16 and 17).On a scale larger than 0.2 mmol, slow addition of carbonate 9f or 9g to a solution of 10, 16 or 17 in DMF at 60 degC was most conducive to formation of allenic derivative 11.Such conditions also supperessed formation of by-products such as carbonate 13a and N⁹-methyladenine (14) observed in the case of methyl carbonate 9f.Intermediates 11 and 12 were deprotected using BCl3 in CH2Cl2 to give 3'-hydroxymethyladenallene (4a) and diol 15, respectively.Compound 4a was deaminated with adenosine deaminase.