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Insight into the Ferrier Rearrangement by Combining Flash Chemistry and Superacids
Author(s) -
Bhuma Naresh,
Lebedel Ludivine,
Yamashita Hiroki,
Shimizu Yutaka,
Abada Zahra,
Ardá Ana,
Désiré Jérôme,
Michelet Bastien,
MartinMingot Agnès,
AbouHassan Ali,
Takumi Masahiro,
Marrot Jérôme,
JiménezBarbero Jesús,
Nagaki Aiichiro,
Blériot Yves,
Thibaudeau Sébastien
Publication year - 2021
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.202010175
Subject(s) - superacid , chemistry , glycosyl , alkyl , ionic bonding , glycoside , organic chemistry , computational chemistry , ion , catalysis
The transformation of glycals into 2,3‐unsaturated glycosyl derivatives, reported by Ferrier in 1962, is supposed to involve an α,β unsaturated glycosyl cation, an elusive ionic species that has still to be observed experimentally. Herein, while combination of TfOH and flow conditions failed to observe this ionic species, its extended lifetime in superacid solutions allowed its characterization by NMR‐based structural analysis supported by DFT calculations. This allyloxycarbenium ion was further exploited in the Ferrier rearrangement to afford unsaturated nitrogen‐containing C ‐aryl glycosides and C ‐alkyl glycosides under superacid and flow conditions, respectively.