Alkynyl and phosphonyl substituted nucleobases: A case of thermally induced conformational polymorphism

Abstract

Substituted nucleobases with alkynyl and phosphonyl groups were investigated in the context of supramolecular interactions and possible use toward synthesis of nucleoside phosphonic acids (NPAs). The adeninyl compound (adeninyl-N-9)-CH2CH2CH2CH2C-CH exhibits conformational polymorphism as revealed by X-ray structures determined at 200 and 298 K. Interestingly, in the compound (adeninyl-N-9)-(CH 2)15CH3, the long aliphatic carbon chain does not show disorder. A rather unusual bending of alkyl chain, likely due to C-H•••O interactions, is observed in the case of the thymine compound (thyminyl)-CH2CH2CH2C-CH that possesses a terminal alkyne group. The powerful hydrogen bond acceptor property of the phosphoryl oxygen (P-O) does not perturb (unless assisted by other hydrogen bonding partners) the homo base-pairing in the structures of most of the phosphonyl substituted nucleobases studied. © 2011 American Chemical Society.