Di Fabio Giovanni, Randazzo Antonio, D'Onofrio Jennifer, Ausín Cristina, Pedroso Enrique, Grandas Anna, De Napoli Lorenzo, Montesarchio Daniela
Dipartimento di Chimica Organica e Biochimica, Università degli Studi di Napoli Federico II, Complesso Universitario di Monte S. Angelo, via Cynthia, 4, I-80126 Napoli, Italy.
J Org Chem. 2006 Apr 28;71(9):3395-408. doi: 10.1021/jo0600757.
CyPLOS (cyclic phosphate-linked oligosaccharides), that is, novel cyclic oligosaccharide surrogates, consisting of two, three, and four phenyl-beta-D-glucopyranoside units, 4,6-linked through stable phosphodiester bonds, were prepared by a straightforward and efficient solid-phase protocol. The assembly of the linear precursors was achieved by standard phosphoramidite chemistry on an automated DNA synthesizer, using a suitably protected 4-phosphoramidite derivative of D-glucose as the building block. For the crucial cyclization step a phosphotriester methodology was exploited, followed by a mild basic treatment releasing the desired cyclic molecules in solution in a highly pure form. The cyclic dimer and trimer were also independently prepared by classical solution synthesis, basically following the same approach. The solution structural preferences of the cyclic dimer and trimer, obtained by detailed NMR analysis, are also reported.
环磷连接寡糖（CyPLOS），即新型环状寡糖替代物，由两个、三个和四个苯基-β-D-吡喃葡萄糖苷单元通过稳定的磷酸二酯键在4,6位连接而成，通过一种直接且高效的固相方法制备。线性前体的组装通过在自动DNA合成仪上使用标准亚磷酰胺化学方法实现，使用适当保护的D-葡萄糖4-亚磷酰胺衍生物作为构建单元。对于关键的环化步骤，采用了磷酸三酯方法，随后进行温和的碱处理，以高纯度形式在溶液中释放出所需的环状分子。环状二聚体和三聚体也通过经典的溶液合成法独立制备，基本遵循相同的方法。还报道了通过详细的核磁共振分析获得的环状二聚体和三聚体的溶液结构偏好。
