Stereocontrolled intramolecular aziridination of glycals: ready access to aminoglycosides and mechanistic insights from DFT studies.
Stereocontrolled intramolecular aziridination of the glycal-derived sulfamates offers a highly efficient strategy to divergently prepare aminoglycosides. Rhodium-catalyzed nitrogen-atom transfer to C==C bonds formed semistable aziridines, which were subjected to various nucleophiles (C, O, S, and N) to give cyclic sulfamate-containing aminosugar derivatives selectively. The second nucleophilic displacement of sulfonyloxy moieties of [1,2,3]-oxathiazepane-2,2- dioxides allows straightforward access to aminoglycosides with selective alpha- or beta-linkages. This approach is operationally simple, complements existing methods, and is a versatile protocol for the synthesis of polyfunctionalized amino sugars. In addition, the mechanism of the rhodium-catalyzed intramolecular aziridination of glycals and its ring-opening reaction was extensively studied by using DFT calculations.
Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 1 Nanyang Walk, Singapore 637616, Singapore.
Rujee
R
Lorpitthaya
Zhi-Zhong
ZZ
Xie
Jer-Lai
JL
Kuo
Xue-Wei
XW
Liu
D000465:Algorithms; D000617:Aminoglycosides / Q000138:chemical synthesis*; D000900:Anti-Bacterial Agents / Q000138:chemical synthesis*; D001388:Aziridines / Q000737:chemistry*; D002384:Catalysis; D008956:Models, Chemical; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism; D013450:Sulfones / Q000737:chemistry; D013451:Sulfonic Acids / Q000737:chemistry; D013830:Thiadiazoles / Q000737:chemistry
D000617:Aminoglycosides; D000900:Anti-Bacterial Agents; D001388:Aziridines; D013450:Sulfones; D013451:Sulfonic Acids; D013830:Thiadiazoles; C005741:sulfamic acid; D012238:Rhodium