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Stereocontrolled Intramolecular Aziridination of Glycals: Ready Access to Aminoglycosides and Mechanistic Insights from DFT Studies
Author(s) -
Lorpitthaya Rujee,
Xie ZhiZhong,
Kuo JerLai,
Liu XueWei
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200701288
Subject(s) - intramolecular force , chemistry , glycal , nucleophile , rhodium , ring (chemistry) , combinatorial chemistry , aziridine , intramolecular reaction , stereochemistry , catalysis , organic chemistry , stereoselectivity
Stereocontrolled intramolecular aziridination of the glycal‐derived sulfamates offers a highly efficient strategy to divergently prepare aminoglycosides. Rhodium‐catalyzed nitrogen‐atom transfer to CC 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 α‐ or β‐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.