Insight into the Ferrier Rearrangement by Combining Flash Chemistry and Superacids

Media type: E-Article
Title: Insight into the Ferrier Rearrangement by Combining Flash Chemistry and Superacids
Contributor: Bhuma, Naresh; Lebedel, Ludivine; Yamashita, Hiroki; Shimizu, Yutaka; Abada, Zahra; Ardá, Ana; Désiré, Jérôme; Michelet, Bastien; Martin‐Mingot, Agnès; Abou‐Hassan, Ali; Takumi, Masahiro; Marrot, Jérôme; Jiménez‐Barbero, Jesús; Nagaki, Aiichiro; Blériot, Yves; Thibaudeau, Sébastien
imprint: Wiley, 2021
Published in: Angewandte Chemie
Language: English
DOI: 10.1002/ange.202010175
ISSN: 1521-3757; 0044-8249
Keywords: General Medicine
Origination:
Footnote:
Description: <jats:title>Abstract</jats:title><jats:p>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 <jats:italic>C</jats:italic>‐aryl glycosides and <jats:italic>C</jats:italic>‐alkyl glycosides under superacid and flow conditions, respectively.</jats:p>

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