光学纯γ肽核酸单体的合成：一项比较研究。
Synthesis of optically pure γPNA monomers: a comparative study.
作者信息
Manna Arunava, Rapireddy Srinivas, Sureshkumar Gopalsamy, Ly Danith H
机构信息
Department of Chemistry and Center for Nucleic Acids Science and Technology (CNAST), Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213.
出版信息
Tetrahedron. 2015 May 27;71(21):3507-3514. doi: 10.1016/j.tet.2015.03.052. Epub 2015 Mar 20.
Abstract
We report a systematic study examining two synthetic routes, reductive amination and Mitsunobu coupling, for preparation of chiral γ-peptide nucleic acid (γPNA) monomers and oligomers. We found that the reductive amination route is prone to epimerization, even under mild experimental conditions. The extent of epimerization could be minimized by utilizing a bulky protecting group such as PhFl; however, it is difficult to remove in the subsequent oligomer synthesis stage. On the other hand, we found that the Mitsunobu route produced optically superior products using standard carbamate protecting groups.
摘要
我们报告了一项系统研究，该研究考察了用于制备手性γ-肽核酸（γPNA）单体和寡聚物的两种合成路线，即还原胺化反应和光延反应。我们发现，即使在温和的实验条件下，还原胺化路线也容易发生差向异构化。通过使用诸如苯基荧光素（PhFl）这样的庞大保护基团，可以将差向异构化的程度降至最低；然而，在随后的寡聚物合成阶段很难将其除去。另一方面，我们发现光延反应路线使用标准的氨基甲酸酯保护基团可产生光学性能更优的产物。
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