287104-72-7Relevant academic research and scientific papers
Enantioselective toluene dioxygenase catalysed di- and tri-hydroxylation of monosubstituted benzenes
Boyd, Derek R.,Sharma, Narain D.,Bowers, Nigel I.,Duffy, John,Harrison, John S.,Dalton, Howard
, p. 1345 - 1350 (2000)
Asymmetric cis-dihydroxylation to yield diols 2A-2G and sequential benzylic monohydroxylation-cis-dihydroxylation to yield triols 4A-4G (trihydroxylation), occurred during biotransformation of a series of monosubstituted alkylbenzene substrates 1A-1G using toluene dioxygenase, a biocatalyst present in Pseudomonas putida UV4. Dioxygenase-catalysed cis-dihydroxylation of the R and S benzylic alcohol enantiomers 3B-3D, 3B′-3D′ gave the corresponding enantiopure triols 4B-4D, 4B′-4D′. Biotransformation of substrates 1J-1L yielded cis-diols 2J-2L and a minor triol metabolite 4A. Benzylic alcohols 3J-3L were postulated as unstable intermediates yielding triol 4A via benzaldehyde 5 and benzyl alcohol 3A intermediates, cis-Dihydroxylation of monosubstituted benzylic substrates containing bulky groups (1H, 1I) or 1,4-dialkyl-substituted benzene substrates (10A-10C) gave the corresponding cis-dihydrodiol metabolites (2H, 2I, 11A-11C) exclusively. The cis-diols 2A-2L, 11A-11C and triols 4A-4F, 4B′-4D′ were stereochemically assigned as single enantiomers of 1S,2R-configuration based on NMR and CD spectroscopy. The absolute configurations of the exocylic chiral centres in the triol bioproducts 4A-4F, 4B′-4D′ were established by stereochemical correlation and aromatisation/hydrogenation to yield the corresponding enantiopure phenolic benzylic alcohols having similar CD spectra.
