Tamura Masazumi, Yuasa Naoto, Cao Ji, Nakagawa Yoshinao, Tomishige Keiichi
Graduate School of Engineering, Tohoku University, Aoba 6-6-07, Aramaki, Aoba-ku, Sendai, Miyagi, 980-8579, Japan.
Angew Chem Int Ed Engl. 2018 Jul 2;57(27):8058-8062. doi: 10.1002/anie.201803043. Epub 2018 Jun 6.
Transformation of sugars, while maintaining the intrinsic stereochemical structure, is desirable. However, such a transformation requires multistep synthesis with protection and deprotection of the OH groups. Herein, a new method for selective transformation of sugar derivatives into chiral building blocks and a diol synthon, with retention of the intrinsic configuration (stereo- and regioselectively), is demonstrated. The method is based on the selective recognition of cis-vicinal OH groups in sugars and leads to the one-pot removal of the cis-vicinal OH groups, without protection of OH groups (except the OH group of the hemiacetal group), over a heterogeneous CeO -supported ReO and Pd (ReO -Pd/CeO ) catalyst by using H as a reducing agent.
在保持固有立体化学结构的同时对糖类进行转化是很有必要的。然而，这种转化需要通过对羟基进行保护和脱保护的多步合成。在此，展示了一种将糖衍生物选择性转化为手性结构单元和二醇合成子的新方法，该方法能保留固有构型（立体和区域选择性）。该方法基于对糖类中顺式邻位羟基的选择性识别，通过使用氢气作为还原剂，在非均相的氧化铈负载的氧化铼和钯（ReO -Pd/CeO ）催化剂上，无需对羟基进行保护（半缩醛基团的羟基除外），一步去除顺式邻位羟基。
