Dipartimento Farmaco-Chimico, University of Messina, Via SS. Annunziata, Messina 98168, Italy.
J Org Chem. 2010 May 7;75(9):2798-805. doi: 10.1021/jo902485m.
A new template of C-4'-truncated phosphonated nucleosides (TPCOANs) has been obtained in good yields according to two different routes which exploit the reactivity of a phosphonated nitrone. The one-step procedure based on the 1,3-dipolar cycloaddition of a phosphonated nitrone with vinyl nucleobases leads to the unnatural alpha-nucleosides as the main adducts. On the other hand, the target beta-anomers have been obtained in high yield by a two-step procedure based on the 1,3-dipolar cycloaddition of a phosphonated nitrone with vinyl acetate followed by nucleosidation reaction. The reactivity of the phosphonated nitrone has been investigated trough quantum mechanical DFT calculations at the B3LYP/D95+(d,p) theory level. Preliminary biological assays show that beta-anomers of TPCOANs are able to inhibit the reverse transcriptase of different retroviruses at concentrations in the nanomolar range, with a potency comparable with that of tenofovir.
已根据两种不同的路线获得了 C-4′-截断膦酸化核苷(TPCOAN)的新模板,这些路线利用了膦酸化硝酮的反应性。基于膦酸化硝酮与乙烯基核苷碱基的 1,3-偶极环加成的一步法导致非天然的α-核苷作为主要加成物。另一方面,通过基于膦酸化硝酮与醋酸乙烯酯的 1,3-偶极环加成 followed by nucleosidation 反应的两步法,可以以高产率获得目标β-异构体。通过在 B3LYP/D95+(d,p)理论水平下进行量子力学 DFT 计算研究了膦酸化硝酮的反应性。初步的生物学测定表明,TPCOAN 的β-异构体能够以纳摩尔浓度抑制不同逆转录病毒的逆转录酶,其效力可与替诺福韦相当。