Controlled dealkylation by BBr3: efficient synthesis of para-alkoxy-phenols

Ether Cleavage Re‐Investigated: Elucidating the Mechanism of BBr3‐Facilitated Demethylation of Aryl Methyl Ethers

“…We began our investigation using standard conditions10 for this reaction: CH 2 Cl 2 as the reaction solvent, near ambient temperature, and a reaction time of ca. 18 h. However, the reaction solvent was varied from CH 2 Cl 2 to CDCl 3 for NMR analysis and to o -dichlorobenzene for the high temperature reactions.…”

“…In order to validate our computational predictions, we aimed to reproduce and expand the findings disclosed in the original methodology report by varying the BBr 3 :anisole ratio. We began our investigation using standard conditions [10] for this reaction: CH 2 Cl 2 as the reaction solvent, near ambient temperature, and a reaction time of ca. 18 h. However, the reaction solvent was varied from CH 2 Cl 2 to CDCl 3 for NMR analysis and to o-dichlorobenzene for the high temperature reactions.…”

“…While there is no shortage in the diversity of BBr 3 -mediated reactions, many of the mechanisms for these transformations have not been fully elucidated. In this report we investigate the mechanism of ether cleavage by BBr 3 5–10 in anisole.…”

“…[4] While there is no shortage in the diversity of BBr 3 -mediated reactions, many of the mechanisms for these transformations have not been fully elucidated. In this report we investigate the mechanism of ether cleavage by BBr 3 [5][6][7][8][9][10] in anisole. Conceptually, demethylation of anisole is initiated by the formation of an ether adduct 1 followed by the loss of bromide.…”

Biocatalytic Methyl Ether Cleavage: Characterization of the Corrinoid‐Dependent Methyl Transfer System from Desulfitobacterium hafniense

“…[2][3] Since O-methyl groups are rather stable and thus more resistant to hydrolysis/cleavage, classical procedures for the cleavage of CÀ O-bonds of methyl ethers usually involve the presence of strong Bronsted [4][5][6][7] or Lewis acids. [8][9][10] Alternatively, the use of metal catalysts [11][12] or nucleophilic methods employing sodium thiolates [13][14][15] belong to the most commonly applied chemical techniques. Ether cleavage is also prevalent in nature, where O-demethylation is part of many aspects of life.…”