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Vessel Effect in C–F Bond Activation Prompts Revised Mechanism and Reveals an Autocatalytic Glycosylation
Author(s) -
Nielsen Michael M.,
Qiao Yan,
Wang Yingxiong,
Pedersen Christian M.
Publication year - 2020
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201901755
Subject(s) - chemistry , autocatalysis , borosilicate glass , fluoride , reaction mechanism , glycosyl , hydrogen bond , glycosylation , leaching (pedology) , inorganic chemistry , catalysis , medicinal chemistry , organic chemistry , molecule , soil water , biochemistry , environmental science , soil science
Activation of C–F bonds under acidic conditions results in the formation of hydrogen fluoride as the reaction progresses. In the following communication, the effect of the vessel material on such reactions has been investigated and a significant difference between an HF‐resistant material and common borosilicate glassware has been found. HF was found to react rapidly with borosilicate glassware, seemingly leaching fluorosilicate into solution, but persisted in HF‐resistant materials. Several examples of C–F bond activation on glycosyl fluorides and benzyl fluorides as well as NMR‐studies suggest a significant effect of the choice of the reaction vessel, leading to the discovery of an autocatalytic glycosylation and a revised mechanism for the activation of benzyl fluorides, suggesting activation by SiF 4 rather than HF.