Ring hydroxylation

Rieske-type clusters are found in aromatic-ring hydroxylating dioxygenase systems (20). These enzymes catalyze the conversion of different aromatic compounds into cis-arene diols ... 

The conversion of tyrosine to epinephrine requires four sequential steps (1) ring hydroxylation (2) decarboxylation (3) side chain hydroxylation to form norepinephrine and (4) N-methylation to form epinephrine. The biosynthetic pathway and the enzymes involved are illustrated in Figure 42-10. 

Atrazine is successively transformed to 2,4,6-trihydroxy-l,3,5-triazine (Pelizzetti et al. 1990) by dealkylation of the alkylamine side chains and hydrolytic displacement of the ring chlorine and amino groups (Figure 1.3). A comparison has been made between direct photolysis and nitrate-mediated hydroxyl radical reactions (Torrents et al. 1997) the rates of the latter were much greater under the conditions of this experiment, and the major difference in the products was the absence of ring hydroxylation with loss of chloride. 

The oxidation of benzene to phenol and 1,4-dihydroxybenzene (Figure 2.11a) (Hyman et al. 1985), both side chain and ring oxidation of ethyl benzene, and ring-hydroxylation of halogenated benzenes and nitrobenzene (Keener and Arp 1994). 

Krivobok S, S Kuony, C Meyer, M Louwagie, JC Wilson, Y Jouanneau (2003) Identification of pyrene-induced proteins m Mycobacterium sp. strain 6PY1 evidence for two ring-hydroxylating dioxygenases. 

Martin VJJ, WW Mohn (1999) A novel aromatic ring-hydroxylating dioxygenase from the diterpenoiddegrading Pseudomonas abietaniphila BKME-9. J Bacteriol 181 2675-2682. 

The A-type proanthocyanidins are characterized by a second ether linkage between an A-ring hydroxyl group of the lower unit and C-2 of the upper unit. Since they are less frequently isolated from plants than the B-types, they have been considered unusual structures [18,19]. The first identified A-type proanthocyanidin was procyanidin A2 isolated from the shells of fruit of Aes-culus hippocastanum. Since then, many more A-type proanthocyanidins have been found in plants, including dimers, trimers, tetramers, pentamers and ethers [18,21]. 

Lonza, for example, has commercialized processes for highly chemo- and regioselective microbial ring hydroxylation and side-chain oxidation of heteroaromatics (see Fig. 2.32 for examples) (Kiener, 1995, 1999). The pharmaceutical intermediate 5-methylpyrazine-2-carboxylic acid, for example, is manufactured by microbial oxidation of 2,5-dimethylpyrazine. Many conversions of the type shown in Fig. 2.32 would not be possible by conventional chemical means. 

Most phenolic compounds are readily oxidized at carbon electrodes. The oxidation potentials vary widely depending upon the number of ring hydroxyl groups and their positions on the ring. Many compounds of biomedical and industrial interest are phenolic and LCEC based trace determinations are quite popular. 

Inspired by the results of aromatic-ring hydroxylation from the laboratory of Karlin and co-workers, a few groups provided further examples of such reactivity, including some structurally characterized complexes of modified m-xylyl-based pyridine-donor ligands (Schiff base and non-Schiff base acyclic ligands), as well as aliphatic amine donor ligands (179) (Cu-Cu 2.990 A),169 (180) (Cu-Cu 3.015 A),170 and (181) (Cu-Cu 2.999 A).171 172 A m-xylyl-based ligand system that was used by Mukherjee and co-workers in the formation of complex (181) also resulted in the isolation of a bis(/i-hydroxo)dicopper(II) complex (182) (Cu-Cu 3.004 A).171,172 Casella and co-workers demonstrated that when their dicopper(I) complex... 

The steroid ring hydroxylation proceeds with the involvement of the monooxygen-ase chain of endoplasmic reticulum membranes. 

Increased Efficiency of Aromatic-Ring Hydroxylating Dioxygenases... 

Butler, C.S. and Mason, J.R. (1997) Structure-function analysis of the bacterial aromatic ring-hydroxylating dioxygenases. Advances in Microbial Physiology, 38, 47-84. 

Gibberellins Growth, complex 5-ring hydroxylated alicycle. Requires iron containing enzyme for synthesis... 

Recently, the mechanism of 6-nitro-BaP ring hydroxylation has been elucidated by using 3-deutero-6-nitro-BaP (144). When incubated with 3-methylcholanthrene-induced rat liver microsomes, this deuterated analogue yielded the same metabolite profile previously observed with 6-nitro-BaP. Spectroscopic analysis of 3-hydroxy-6-nitro-BaP and 6-nitro-BaP-3,9-hydroquinone indicated that 30% of the deuterium label had migrated to carbon 2, presumably via an NIH shift. Therefore, it appears that 6-nitro-BaP-2,3-oxide is a common intermediate for these two metabolites. 

Aromatic amines are initially metabolized by aromatic and A -hydroxylation (oxidation reactions) and Y-acetylation. Following aromatic ring hydroxylation, the ring structure may be further conjugated with glucuronic acid or sulfate (Parkinson 1996). N-hydroxylation results in the potential methemoglobin-generating metabolite,... 

The selective hydroxylation, in the presence of aqueous H2O2, of aromatic hydrocarbons such as benzene, toluene, and xylene to phenol, cresols, and xylenols, respectively, occurs easily on TS-1 (33,165,224). Again, a significant contrast between TS-2 and VS-2 in the oxidation of toluene is that when the catalyst is the former, only aromatic ring hydroxylation takes place, although when the catalyst is VS-2, the side chain C-H bonds are also hydroxylated (165, 218,219,225,226) (Table XXVIII). 

---