Premium
Enzyme‐Catalysed Synthesis of Cyclohex‐2‐en‐1‐one cis ‐Diols from Substituted Phenols, Anilines and Derived 4‐Hydroxycyclohex‐2‐en‐1‐ones
Author(s) -
Boyd Derek R.,
Sharma Narain D.,
McIntyre Peter B. A.,
Stevenson Paul J.,
McRoberts W. Colin,
Gohil Amit,
Hoering Patrick,
Allen Christopher C. R.
Publication year - 2017
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201700711
Subject(s) - chemistry , pseudomonas putida , tautomer , phenols , stereochemistry , phenol , hydroquinone , diol , toluene , dioxygenase , organic chemistry , aniline , enzyme
Toluene dioxygenase‐catalysed cis ‐dihydroxylations of substituted aniline and phenol substrates, with a Pseudomonas putida UV4 mutant strain and an Escherichia coli pCL‐4t recombinant strain, yielded identical arene cis ‐dihydrodiols, which were isolated as the preferred cyclohex‐2‐en‐1‐one cis ‐diol tautomers. These cis ‐diol metabolites were predicted by preliminary molecular docking studies, of anilines and phenols, at the active site of toluene dioxygenase. Further biotransformations of cyclohex‐2‐en‐1‐one cis ‐diol and hydroquinone metabolites, using Pseudomonas putida UV4 whole cells, were found to yield 4‐hydroxycyclohex‐2‐en‐1‐ones as a new type of phenol bioproduct. Multistep pathways, involving ene reductase‐ and carbonyl reductase‐catalysed reactions, were proposed to account for the production of 4‐hydroxycyclohex‐2‐en‐1‐one metabolites. Evidence for the phenol hydrate tautomers of 4‐hydroxycyclohex‐2‐en‐1‐one metabolites was shown by formation of the corresponding trimethylsilyl ether derivatives.