Mechanistic study on regioselective oxygenation reaction of 1,2-quinones with peroxybenzoic acids: Relevant to mechanisms of catecholdioxygenases

Hitomi, Yutaka; Yoshida, Hiroshi; Tanaka, Tsunehiro; Funabiki, Takuzo

doi:10.1016/j.molcata.2006.02.002

Cited by 6 publications

(5 citation statements)

References 46 publications

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“…14 Physical organic chemistry studies on the reaction of 1,2-quinones with peroxybenzoic acids have also provided evidence that the mechanism of cleavage of the O-O bond dictates the regioselectivity of the cleavage reaction. 18 Using the TACN extradiol model reaction, it is possible to examine the effects of changing the pK a of the acid-base catalyst. The Brønsted plot shown in Fig.…”

Section: Discussionmentioning

confidence: 99%

Investigation of acid–base catalysis in the extradiol and intradiol catechol dioxygenase reactions using a broad specificity mutant enzyme and model chemistry

et al. 2009

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The extradiol and intradiol catechol dioxygenase reaction mechanisms proceed via a common proximal hydroperoxide intermediate, which is processed via different Criegee 1,2-rearrangements. An R215W mutant of extradiol dioxygenase MhpB, able to produce a mixture of extradiol and intradiol cleavage products, was analysed at pH 5.2-8.6, and the yield of extradiol product was found to be highly pH-dependent, whereas the yield of intradiol product was pH-independent. The acid-base chemistry of a biomimetic reaction for extradiol oxidative catechol cleavage was also investigated, using 1,4,7-triazacyclononane, FeCl(2), and pyridine in methanol, in which pyridine is proposed to act as both a general base and (in protonated form) a general acid. Kinetic experiments using a range of meta- and para-substituted pyridines gave a Brønsted plot of log(v) vs. pK(a) showing a bell-shaped plot. Oxidative catechol cleavage by a pyridine-monosubstituted beta-cyclodextrin in the presence of TACN and FeCl(2) in methanol yielded only intradiol cleavage products. It is therefore proposed that bifunctional acid-base catalysis is required for iron (ii)-dependent extradiol catechol cleavage, whereas the rate-determining step for intradiol catechol cleavage does not involve acid-base catalysis.

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Section: Discussionmentioning

confidence: 99%

Investigation of acid–base catalysis in the extradiol and intradiol catechol dioxygenase reactions using a broad specificity mutant enzyme and model chemistry

et al. 2009

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“…Despite the fact that the Baeyer–Villiger reaction is known since 1899, the mechanism of this reaction is still not fully understood. The nature of the acid catalyst [ 220 ] and the type of O–O-bond cleavage in the Criegee intermediate [ 221 ] were found to play an important role in this reaction. Probably the hydrogen bonds in Baeyer–Villiger reactions play an important role [ 222 ].…”

Section: Reviewmentioning

confidence: 99%

“…The dependence of the course of the Baeyer–Villiger oxidation on the type of O−O-bond cleavage in the Criegee intermediate was studied in the oxidation reaction of 1,2-quinone 18 with perbenzoic acid [ 221 ]. The reaction gave two oxidation products – anhydride 20 and the seven-membered α-ketolactone 21 .…”

Section: Reviewmentioning

confidence: 99%

Rearrangements of organic peroxides and related processes

Yaremenko¹,

Vil²,

Demchuk³

et al. 2016

Beilstein J. Org. Chem.

193

136

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SummaryThis review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

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“…15 The latter study assumed a protonation of the proximal oxygen atom by a bound water molecule, 15 which will assist the Criegee rearrangement pathway. Our experimental results are not consistent with a direct Criegee rearrangement; therefore, further modeling studies on these mechanisms might reveal the effects that the precise geometry of the hydroperoxide complex and the positioning of active-site residues have on the OsO 29 Extradiol dioxygenase enzyme MhpB, in contrast, processed 6-hydroxymethyl-6-methylcyclohexa-2,4-dienone(2)into2-tropolone, via a pinacol rearrangement involving a 1,2-alkenyl migration. This is entirely consistent with the expected Criegee rearrangement mechanism for extradiol dioxygenase cleavage, which is believed to occur through 1,2-alkenyl migration, assisted by acid-base catalysis.…”

Section: Discussionmentioning

confidence: 56%

“…Our experimental results are not consistent with a direct Criegee rearrangement; therefore, further modeling studies on these mechanisms might reveal the effects that the precise geometry of the hydroperoxide complex and the positioning of active-site residues have on the OO homolysis versus Criegee rearrangement pathways. Evidence in favor of an OO bond homolysis mechanism in model intradiol cleavage reactions has been reported by Hitomi et al, via study of substituent effects and solvent dependence …”

Section: Discussionmentioning

confidence: 79%

Evidence from Mechanistic Probes for Distinct Hydroperoxide Rearrangement Mechanisms in the Intradiol and Extradiol Catechol Dioxygenases

Xin

Bugg

2008

J. Am. Chem. Soc.

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Three mechanistic probes were used to investigate whether the Criegee rearrangement step of catechol 1,2-dioxygenase (CatA) from Acinetobacter sp. proceeds via a direct 1,2-acyl migration, via homolytic O-O cleavage, or via a benzene oxide-oxepin rearrangement. Incubation of CatA with 3-chloroperoxybenzoic acid led to the formation of a 9:1 mixture of 2-chlorophenol and 3-chlorophenol, via a mechanism involving O-O homolytic cleavage. Incubation of CatA with 2-hydroperoxy-2-methylcyclohexanone led to formation of 5,6-diketoheptan-1-ol, also consistent with an O-O homolytic cleavage mechanism, and not consistent with a direct 1,2-acyl migration. No reaction product was isolated from incubation of CatA with 6-hydroxymethyl-6-methylcyclohexa-2,4-dienone, an analogue that is able to undergo the benzene oxide-oxepin rearrangement, but not able to undergo O-O homolytic cleavage. In contrast, incubation of extradiol dioxygenase MhpB from Escherichia coli with 6-hydroxymethyl-6-methylcyclohexa-2,4-dienone led to the formation of a 2-tropolone ring expansion product, consistent with a direct 1,2-alkenyl migration for extradiol cleavage. Taken together, the results imply different mechanisms for the Criegee rearrangement steps of intradiol and extradiol catechol dioxygenases: a direct 1,2-alkenyl migration for extradiol cleavage and an O-O homolytic cleavage mechanism for intradiol cleavage.

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Mechanistic study on regioselective oxygenation reaction of 1,2-quinones with peroxybenzoic acids: Relevant to mechanisms of catecholdioxygenases

Cited by 6 publications

References 46 publications

Investigation of acid–base catalysis in the extradiol and intradiol catechol dioxygenase reactions using a broad specificity mutant enzyme and model chemistry

Investigation of acid–base catalysis in the extradiol and intradiol catechol dioxygenase reactions using a broad specificity mutant enzyme and model chemistry

Rearrangements of organic peroxides and related processes

Evidence from Mechanistic Probes for Distinct Hydroperoxide Rearrangement Mechanisms in the Intradiol and Extradiol Catechol Dioxygenases

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