title: Convenient syntheses of 3'-amino-2',3'-dideoxynucleosides, their 5'-monophosphates, and 3'-aminoterminal oligodeoxynucleotide primers.
abstract: 5'-Protected 3'-amino-2',3'-dideoxynucleosides containing any of the four canonical nucleobases (A/C/G/T) were prepared via azides in five to six steps, starting from deoxynucleosides. For pyrimidines, the synthetic route involved nucleophilic opening of anhydronucleosides. For purines, an in situ oxidation/reduction sequence, followed by a Mitsunobu reaction with diphenyl-2-pyridylphosphine and sodium azide, provided the 3'-azidonucleosides in high yield and purity. For solid-phase synthesis of aminoterminal oligonucleotides, aminonucleosides were linked to controlled pore glass through a novel hexafluoroglutaric acid linker. These supports gave 3'-aminoterminal primers in high yield and purity via conventional DNA chain assembly and one-step deprotection/release with aqueous ammonia. Primers thus prepared were successfully tested in enzyme-free chemical primer extension, an inexpensive methodology for genotyping and labeling. Protected 5'-monophosphates of 3'-amino-2',3'-dideoxynucleosides were also prepared, providing starting materials for the preparation of labeled or photolably protected monomers for chemical primer extension.
authors.affiliation: Institute for Organic Chemistry, University of Karlsruhe (TH), 76131 Karlsruhe, Germany.
authors.forename: Ralf
authors.initials: R
authors.lastname: Eisenhuth
authors.forename: Clemens
authors.initials: C
authors.lastname: Richert
mesh_terms: D015224:Dideoxynucleosides / Q000138:chemical synthesis* / Q000737:chemistry; D015226:Dinucleoside Phosphates / Q000138:chemical synthesis* / Q000737:chemistry; D009690:Nucleic Acid Conformation; D009838:Oligodeoxyribonucleotides / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D015224:Dideoxynucleosides; D015226:Dinucleoside Phosphates; D009838:Oligodeoxyribonucleotides