title: A Migratory Ether Formation Route to Medium-Sized Sugar Mimetics.
abstract: 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.
authors.affiliation: Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, China.
authors.forename: Hao
authors.initials: H
authors.lastname: Jiang
authors.affiliation: Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, China.|School of Chemical Engineering, Shandong University of Technology, Zibo, 255049, P. R. China.
authors.forename: Li-Ping
authors.initials: LP
authors.lastname: Xu
authors.affiliation: Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, China.
authors.forename: Yan
authors.initials: Y
authors.lastname: Fang
authors.affiliation: Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, China.
authors.forename: Zhen-Xing
authors.initials: ZX
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, China. zyang@pku.edu.cn.
authors.forename: Zhen
authors.initials: Z
authors.lastname: Yang
authors.affiliation: Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, China. huangyong@pkusz.edu.cn.
authors.forename: Yong
authors.identifier: 0000-0001-8377-8923
authors.initials: Y
authors.lastname: Huang
keywords: medium-sized rings; migratory ether formation; ring-opening reactions; sugar; trimethyl alumininum