A Migratory Ether Formation Route to Medium-Sized Sugar Mimetics

作者：Jiang, Hao; Xu, Li-Ping; Fang, Yan; Zhang, Zhen-Xing; Yang, Zhen^*; Huang, Yong^*

来源：Angewandte Chemie - International Edition, 2016, 55(46): 14338-14342.

DOI：10.1002/anie.201608974

• medium-sized rings
• migratory ether formation
• ring-opening reactions
• sugar
• trimethyl alumininum

Polyol-substituted cyclic ethers are fundamental building blocks of biomolecules. The position and stereochemistry of multiple hydroxy substituents of cyclic ethers play a central role in their biological function. Current methods for the synthesis of such structures are limited to "naked" ring products with no or few substituents. Here we describe a general route to medium-sized polyol cyclic ethers using a migratory ether formation strategy. In contrast to the common pathway of direct opening of epoxides, Me3Al was found to promote an unprecedented ether addition reaction, opening a neighboring epoxide. The resulting oxonium intermediate triggers a 1,3-methyl shift to yield 2-deoxyribital products. When the hemiacetal auxiliary is a monosaccharide, the sugar ring is expanded by four atoms to give the corresponding 9- to 11-membered analogues. This method provides an entry into the untapped chemical space of medium-sized sugar mimetics.

• 出版日期2016-11-7
• 单位北京大学深圳研究生院; 山东理工大学