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Thiols Act as Methyl Traps in the Biocatalytic Demethylation of Guaiacol Derivatives
Author(s) -
Pompei Simona,
Grimm Christopher,
Schiller Christine,
Schober Lukas,
Kroutil Wolfgang
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.202104278
Subject(s) - guaiacol , chemistry , demethylation , catechol , organic chemistry , yield (engineering) , enzyme , biochemistry , gene expression , dna methylation , gene , materials science , metallurgy
Abstract Demethylating methyl phenyl ethers is challenging, especially when the products are catechol derivatives prone to follow‐up reactions. For biocatalytic demethylation, monooxygenases have previously been described requiring molecular oxygen which may cause oxidative side reactions. Here we show that such compounds can be demethylated anaerobically by using cobalamin‐dependent methyltransferases exploiting thiols like ethyl 3‐mercaptopropionate as a methyl trap. Using just two equivalents of this reagent, a broad spectrum of substituted guaiacol derivatives were demethylated, with conversions mostly above 90 %. This strategy was used to prepare the highly valuable antioxidant hydroxytyrosol on a one‐gram scale in 97 % isolated yield.