...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>ACS Macro Letters >Regioisomeric Preference in Ring-Opening Polymerization of 3 ',5 '-Cyclic Phosphoesters of Functional Thymidine DNA Analogues
【24h】

Regioisomeric Preference in Ring-Opening Polymerization of 3 ',5 '-Cyclic Phosphoesters of Functional Thymidine DNA Analogues

机译：官能胸苷DNA类似物的3'，5' - 环磷酸酯的开环聚合中的测定偏好

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Regioregularity is a crucial property in the synthesis of DNA analogues, as natural DNA is synthesized exclusively in the 5' to 3' direction. We have focused our attention on the determination of the regioisomeric distribution of poly(3',5'-cyclic 3-(3-butenyl) thymidine ethylphosphate)s obtained from the ring-opening polymerization of (R)-3',5'-cyclic 3-(3-butenyl) thymidine ethylphosphate. The regioisomeric preference was investigated by comparison to synthesized model compounds of 3',3'-, 3',5'-, and 5',5'-linkages, where the model 3'-phosphoester linkages were to the secondary alcohol of 3-hydroxytetrahydrofuran and the model 5'-linkages derived from coupling to the primary alcohol of tetrahydrofurfuryl alcohol. From the P-31 resonance frequency assignments of those small molecule model compounds, P-31 NMR spectra revealed the major connectivity in the polymer backbone to be 3',5'-linkages, with = 30% of other isomeric forms. Model reactions employing a series of alcohol initiators imparting various degrees of steric hindrance, to mimic the increased steric hindrance of the propagating alcohol relative to the initiator, were then conducted to afford the corresponding ring-opened unimer adducts and to gain understanding of the regioselectivity during the ring-opening polymerization. H-1-P-31 heteronuclear multiple-bond correlation spectroscopy showed ethanol and 4-methoxybenzyl alcohol initiation to yield only the P-O5' bond cleavage product, whereas attack by isopropyl alcohol upon (R)-3',5'-cyclic 3-(3-butenyl) thymidine ethylphosphate afforded both P-O3' and P-O5' bond cleavage products, supporting our hypothesis that the increased steric hindrance of the propagating species dictates the regioselectivity of the P-O bond cleavage. Further model reactions suggested that the P-O5' bond cleavage products can be detected upon the formation of dimers during the ring-opening polymerization. Overall, this work provides a fundamental understanding of the polymerization behavior of six-membered cyclic phosphoesters and broadens the scope of DNA analogues from the ring-opening polymerization of 3',5'-cyclic phosphoesters.
机译：Regioregularity是在合成DNA类似物中的关键性，因为自然DNA仅在5'至3'方向上合成。我们的注意力对从（R）-3'，5'的开环聚合中获得的聚（3'，5'-环状3-（3-丁烯基）乙基磷酸乙基磷酸盐）S的测定的测定。 - 环3-（3-丁烯基）胸苷乙基磷酸。通过与合成模型化合物的3'，3'-，3'，5'-和5'，5'-键合的比较研究了测定的偏好，其中3'-磷酸酯键是3的二次醇 - 羟基四氢呋喃和模型5'-键源于偶联与四氢糠醇的伯醇的偶联。从那些小分子模型化合物的P-31共振频率分配，P-31 NMR光谱揭示了聚合物主链中的主要连通性为3'，5'-键，其中含量的其他异构形式的30％。采用赋予各种醇引发剂的模型反应赋予各种空间障碍，以模仿相对于引发剂的繁殖醇的增加的空间阻断，得到相应的环形开启的单层加合物，并在此期间获得地区选择性的理解开环聚合。 H-1-P-31异核多键相关光谱显示乙醇和4-甲氧基苄醇引发，仅产生P-O5'键裂解产物，而通过异丙醇侵蚀（R）-3'，5'-环3-（3-丁烯基）胸苷乙基磷酸磷酸，得到P-O3'和P-O5'键裂解产物，支持我们的假设，即繁殖物种的增加的空间阻断决定了PO键切割的区域选择性。进一步的模型反应表明，可以在开环聚合期间在形成二聚体时检测到P-O5'键裂解产物。总体而言，这项工作为六元环磷酸酯的聚合行为提供了基本的理解，并从开环聚合的3'，5'-环状磷酸酯的DNA类似物的范围扩大。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号