New chiral synthons from the microbial oxidation of bromonaphthalenes

Biocatalytic Oxidation Reactions: A Chemist's Perspective

“…TDO:toluene dioxygenase; [44] BDO:benzoate dioxygenase; [45] NDO: naphthalene dioxygenase. [46] Thus far, FMO-catalysed hydroxylations of phenols have been reported to occur only in combination with rearomatisation, hence giving aromatic products.V ery recently,N arayan and co-workers,h owever, reported various FMOs catalysing the oxidative dearomatisation of substituted phenols,g iving access to aw hole world of new synthons for organic synthesis (Scheme 11). [51] Very exciting new reactions may be expected in the future.…”

Metabolism of 2-hydroxy-1-naphthoic acid and naphthalene via gentisic acid by distinctly different sets of enzymes in Burkholderia sp. strain BC1

“…Similarly, dioxygenation of both 1-naphthol and 2-naphthol was reported by a mutant strain of naphthalene-degrading Pseudomonas fluorescens N3 (NCIMB 40530) (Bianchi et al, 1997). Dioxygenation of the unsubstituted ring was also reported for bromonaphthalenes in Pseudomonas putida NCIB 9816/11 (Hudlicky et al, 1996), 2-methylnaphthalene in Sphingomonas paucimobilis 2322 (Dutta et al, 1998) and Pseudomonas putida NCIB 9816/11 (Deluca & Hudlicky, 1990), and 2-methoxynaphthalene by the actions of naphthalene, toluene and biphenyl dioxygenases (Whited et al, 1994).…”

Toluene Dioxygenase‐Catalyzed Synthesis of cis‐Dihydrodiol Metabolites from 2‐Substituted Naphthalene Substrates: Assignments of Absolute Configurations and Conformations from Circular Dichroism and Optical Rotation Measurements

“…The regiochemistries and absolute stereochemistries of seven of the nineteen cis-dihydrodiol metabolites (1 a, 1 c, 1 e, 1 f, 2 c, 3 a, 3 c) had been unequivocally determined earlier. [14][15][16][17][18] NMR analysis (NOE, HMBC, coupling constants) and aromatisation and identification of the known phenolic derivatives were used to ascertain the regiochemistries of all of the cis-dihydrodiols isolated during the current study. The enantiomeric excess (ee) values for all cis-dihydrodiols were found to be > 98 % through the formation of chiral boronate derivatives by methods described earlier.…”

“…[13] However, a marked degree of regioselectivity was observed in bacterial NDO-catalyzed cis-dihydroxylation of acceptable 2-substituted naphthalene substrates (E), with preferential attack occurring at the 7,8bonds to give cis-dihydrodiols of type F (X = Cl, Br, Me, Et, CO 2 Me, OMe, NO 2 ) as major metabolites, (Scheme 1 and Table 1). [14][15][16][17][18] The NDO enzyme present in a mutant strain of Pseudomonas putida (9816/11) was also found to catalyse Abstract: cis-Dihydrodiol metabolites have been isolated from naphthalene and six 2-substituted naphthalene substrates. Their structures and absolute configurations have been determined by a combination of calculated (TDDFT) and experimentally based circular dichroism (CD) and optical rotation (OR) methods.…”

“…Keywords: absolute configuration · bacterial metabolites · circular dichroism · diols · optical rotation [ cis-dihydroxylation at the 5,6-bonds of 2-methoxynaphthalene and 2-bromonaphthalene (E, X= OMe and Br) to give the corresponding cis-dihydrodiols G (X = OMe and Br) as very minor metabolites (< 10 % relative yields). [14,15] Alternative Pseudomonas strains (A3 and C22) expressing a further type of NDO were also found to catalyse cis-dihydroxylation at the 1,2-bonds of the naphthalene rings in the carboxylic acids E (X = CO 2 H and CH 2 CO 2 H) to give isolable cis-dihydrodiols I (X = CO 2 H and CH 2 CO 2 H) as the sole metabolites. [19] It is noteworthy that, to date, only the TDO enzyme has been reported to catalyse cis-dihydroxylation at the 3,4bonds of 2-substituted naphthalenes E (X = Me and OMe) to give cis-dihydrodiols H (X = Me and OMe) as minor metabolites.…”