phosphoramidite and formic-acid

We here report the synthesis of novel modified nucleic acid containing a formyl group and the evaluation of interstrand cross-linking between the modified DNA and the complementary strand. The synthesis of the formyl-containing oligodeoxynucleotide (ODN) was achieved by a post synthetic modification of corresponding ODN containing a 1,2-diol. The ODN containing the diol moiety was successfully synthesized by a standard phosphoramidite method, and was quantitatively converted to the desired formyl-containing ODN by sodium periodate oxidation. Hybridizaiton of the formyl ODN and the complementary ODN produced the interstrand cross-link between the formyl group and N(6)-exocyclic amino group of adenine.

Topics: Adenine; Cross-Linking Reagents; DNA; Formates; Oligodeoxyribonucleotides; Organophosphorus Compounds

The asymmetric synthesis of protected amines via the copper/phosphoramidite-catalyzed addition of organozinc and organoaluminum reagents to N-acylimines, generated in situ from aromatic and aliphatic alpha-amidosulfones, is reported. High yields of optically active N-formyl-protected amines and enantioselectivities up to 99% were obtained. Under the reaction conditions, partial oxidation of the phosphoramidite ligand to the corresponding phosphoric amide was detected. A preliminary study on the origin and the effect on the catalytic addition reaction is presented.

Topics: Catalysis; Copper; Formates; Imines; Ligands; Magnetic Resonance Spectroscopy; Molecular Structure; Organometallic Compounds; Organophosphorus Compounds; Oxidation-Reduction; Stereoisomerism; Sulfonic Acids; Sulfonium Compounds; Toluene