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A Migratory Ether Formation Route to Medium‐Sized Sugar Mimetics
Author(s) -
Jiang Hao,
Xu LiPing,
Fang Yan,
Zhang ZhenXing,
Yang Zhen,
Huang Yong
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201608974
Subject(s) - oxonium ion , polyol , ether , chemistry , epoxide , hemiacetal , ring (chemistry) , monosaccharide , yield (engineering) , sugar , ring size , tetrahydropyran , stereochemistry , organic chemistry , polyurethane , materials science , catalysis , ion , metallurgy
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, Me 3 Al 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.