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Premium Formylation of activated arenes by phenyl formate: implications for the mechanism of the Fries rearrangement of aryl formates
Author(s)
Bagno Alessandro,
Kantlehner Willi,
Saielli Giacomo
Publication year2008
Publication title
journal of physical organic chemistry
Resource typeJournals
PublisherJohn Wiley & Sons
Abstract We present an NMR and DFT investigation of the reaction of phenyl formate with 3‐methoxyphenol and 3,5‐dimethoxyphenol with excess BCl 3 . The products obtained (3‐methoxy‐ and 3,5‐dimethoxy‐salicylaldehyde, respectively) are the same as those resulting from the Fries rearrangement of 3‐methoxy‐ and 3,5‐dimethoxy‐phenyl formate. These results represent a novel regioselective synthetic route to aromatic aldehydes, using phenyl formate as a source of formylating agent. They also unambiguously prove that the Fries rearrangement of aryl formates (that we recently investigated in J. Org. Chem . 71 , 9331–9340, 2006) is intermolecular: the intermediate formyl chloride is released in situ and, in turn, it formylates the intermediate dichloroborate ester of 3‐methoxy‐ and 3,5‐dimethoxy‐phenol in a second independent step. The BCl 2 moiety bound to the aryl oxygen of the substituted phenol interacts with the formyl chloride strongly favouring the ortho substitution. Copyright © 2008 John Wiley & Sons, Ltd.
Subject(s)alkyl , aryl , catalysis , chemistry , formate , formylation , fries rearrangement , medicinal chemistry , moiety , organic chemistry , phenol , regioselectivity , salicylaldehyde , schiff base , stereochemistry
Language(s)English
SCImago Journal Rank0.325
H-Index66
eISSN1099-1395
pISSN0894-3230
DOI10.1002/poc.1356

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