摘要:
A large-scale synthesis was carried out for alkynyl C-nucleotide oligomers in order to clarify the structural details of the artificial DNA. A liquid-phase synthesis by means of phosphoramidite methodology enabled us to handle similar to 0.1 g of the DNA oligomers possessing a pseudouracil derivative (T*) as a non-natural nucleobase. H-1 NMR measurements in aqueous media were carried out for the oligomers, succeeded in the accurate assignments of the protons accompanying with determination of the coupling constants (J values). These J values revealed that average conformation of the alkynylribose rings in the DNA was substantially biased toward the S-type conformers (T-2(1)/E-1/T-0(1)). X-ray crystal analysis of the non-natural nucleoside also supported the S-type conformation (E-2/T-2(1)) as seen in natural B-DNA. (C) 2012 Elsevier Ltd. All rights reserved.