| Title | A Migratory Ether Formation Route to Medium-Sized Sugar Mimetics |
| Authors | Jiang, Hao Xu, Li-Ping Fang, Yan Zhang, Zhen-Xing Yang, Zhen Huang, Yong |
| Affiliation | Peking Univ, Shenzhen Grad Sch, Key Lab Chem Genom, Shenzhen 518055, Peoples R China. Shandong Univ Technol, Sch Chem Engn, Zibo 255049, Peoples R China. |
| Keywords | medium-sized rings migratory ether formation ring-opening reactions sugar trimethyl alumininum 2,3-EPOXY ALCOHOLS ASYMMETRIC EPOXIDATION EPOXY ALCOHOLS EPOXIDES OPENINGS LACTONES RINGS |
| Issue Date | 2016 |
| Publisher | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION |
| Citation | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION.2016,55(46),14338-14342. |
| 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. |
| URI | http://hdl.handle.net/20.500.11897/457124 |
| ISSN | 1433-7851 |
| DOI | 10.1002/anie.201608974 |
| Indexed | SCI(E) PubMed |
| Appears in Collections: | 深圳研究生院待认领 |
