Timosheva Natalya V, Chandrasekaran A, Holmes Robert R
Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003-9336, USA.
J Am Chem Soc. 2005 Sep 14;127(36):12474-5. doi: 10.1021/ja053422n.
The first successful crystal structures of biorelevant nucleoside and carbohydrate-based phosphoranes are reported. Employing thymidine, a nucleotidyl phosphorane was synthesized in 90% yield and was shown by X-ray analysis to possess a trigonal bipyramidal geometry. With the use of 1,2-O-isopropylidene-alpha-d-glucofuranose, a carbohydrate-based phosphorane was formed and similarly found to have a trigonal bipyramidal geometry. NMR studies demonstrated the existence of isomerism in solution associated with the nucleotidyl phosphorane and rapid exchange for the carbohydrate-based phosphorane. The geometrical representations reported here are expected to have significant applications associated with active site mechanisms of phosphoryl transfer enzymes, for example, in DNA, RNA, c-AMP, and others.
报道了具有生物相关性的核苷和基于碳水化合物的磷烷的首个成功晶体结构。使用胸苷，以90%的产率合成了一种核苷酸基磷烷，X射线分析表明其具有三角双锥几何结构。使用1,2-O-异丙叉基-α-D-呋喃葡萄糖，形成了一种基于碳水化合物的磷烷，同样发现其具有三角双锥几何结构。核磁共振研究表明，溶液中存在与核苷酸基磷烷相关的异构现象，且基于碳水化合物的磷烷存在快速交换。本文报道的几何表示预计在磷酸转移酶活性位点机制方面有重要应用，例如在DNA、RNA、环磷酸腺苷等方面。
