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3383-21-9 Usage

Uses

Different sources of media describe the Uses of 3383-21-9 differently. You can refer to the following data:
1. 4,6-Di-tert-butyl-1,2-benzoquinone is a Ortho-Quinone derivative is know to possess a number of biological properties such as antitumoral, antimicrobacterial and anti-cardiovascular disease.
2. 3,5-Di-tert-butyl-o-benzoquinone was used in the preparation of benzoxazoles derivative ligands. It was also used in the preparation of 1,4-benzodioxines via hetero Diels Alder reaction with acyclic dienes.

Synthesis Reference(s)

Tetrahedron, 44, p. 6397, 1988 DOI: 10.1016/S0040-4020(01)89827-6Tetrahedron Letters, 23, p. 957, 1982 DOI: 10.1016/S0040-4039(00)86993-2

General Description

Reactions of the phosphinidene-bridged complexes [Fe2(η5-C5H5)2(μ-PR)(μ-CO)(CO)2] (R = Cy, Ph) with 3,5-di-tert-butyl-o-benzoquinone has been reported.

Purification Methods

It can be recrystallised from MeOH or pet ether, and forms fine red plates or rhombs. [Flaig et al. Justus Liebigs Ann Chem 597 196 1955, IR: Ley & Müller Chem Ber 89 1402 1956, Beilstein 7 IV 2113.]

Check Digit Verification of cas no

The CAS Registry Mumber 3383-21-9 includes 7 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 4 digits, 3,3,8 and 3 respectively; the second part has 2 digits, 2 and 1 respectively.
Calculate Digit Verification of CAS Registry Number 3383-21:
(6*3)+(5*3)+(4*8)+(3*3)+(2*2)+(1*1)=79
79 % 10 = 9
So 3383-21-9 is a valid CAS Registry Number.
InChI:InChI=1/C14H20O2/c1-13(2,3)9-7-10(14(4,5)6)12(16)11(15)8-9/h7-8H,1-6H3

3383-21-9 Well-known Company Product Price

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  • Alfa Aesar

  • (L00169)  3,5-Di-tert-butyl-o-benzoquinone, 98+%   

  • 3383-21-9

  • 5g

  • 443.0CNY

  • Detail
  • Alfa Aesar

  • (L00169)  3,5-Di-tert-butyl-o-benzoquinone, 98+%   

  • 3383-21-9

  • 25g

  • 1777.0CNY

  • Detail

3383-21-9SDS

SAFETY DATA SHEETS

According to Globally Harmonized System of Classification and Labelling of Chemicals (GHS) - Sixth revised edition

Version: 1.0

Creation Date: Aug 19, 2017

Revision Date: Aug 19, 2017

1.Identification

1.1 GHS Product identifier

Product name 3,5-ditert-butylcyclohexa-3,5-diene-1,2-dione

1.2 Other means of identification

Product number -
Other names 3,5-Di-tert-butyl-1,2-benzoquinone

1.3 Recommended use of the chemical and restrictions on use

Identified uses For industry use only.
Uses advised against no data available

1.4 Supplier's details

1.5 Emergency phone number

Emergency phone number -
Service hours Monday to Friday, 9am-5pm (Standard time zone: UTC/GMT +8 hours).

More Details:3383-21-9 SDS

3383-21-9Relevant articles and documents

Oxidation of hindered aniline to iminocyclohexa-2,4-dienone by copper(II) complex of an N-substituted bis-benzimidazolyl ligand

Yadav, Anjana,Mathur, Pavan

, p. 62 - 71 (2015)

Copper(II) complex of an N-octylated bis-benzimidazolyl ligand is synthesized and characterized. X-ray diffraction study revealed that copper(II) is in a distorted square-planar environment of two benzimidazolyl imine nitrogens and two nitrato ligands. This complex carries out the oxidation of 2,4,6-tri-tert-butylaniline at room temperature utilizing low amounts of tert-butylhydroperoxide (TBHP) as an alternate source of oxygen. 3,5-Di-tert-butyl-6-iminocyclohexa-2,4-dienone is found to be the major product along with 3,5-di-tert-butylcyclohexa-3,5-diene-1,2-dione. The oxidation products have been isolated and characterized by 1H NMR, 13C NMR and COSY experiments. The catalytic oxidation proceeds via a copper(II)/copper(III) cycle.

Extradiol oxidative cleavage of catechols by ferrous and ferric complexes of 1,4,7-triazacyclononane: Insight into the mechanism of the extradiol catechol dioxygenases

Lin,Reid,Bugg

, p. 5030 - 5039 (2001)

The major oxygenation product of catechol by dioxygen in the presence of FeCl2 or FeCl3, 1,4,7-triazacyclononane (TACN), and pyridine in methanol is the extradiol cleavage product 2-hydroxymuconic semi-aldehyde methyl ester (Lin, G.; Reid, G.; Bugg, T. D. H. J. Chem. Soc. Chem. Commun. 2000, 1119-1120). Under these conditions, extradiol cleavage of a range of 3- and 4-substituted catechols with electron-donating substituents is observed. The reaction shows a preference in selectivity and rate for iron(II) rather than iron(III) for the extradiol cleavage, which parallels the selectivity of the extradiol dioxygenase family. The reaction also shows a high selectivity for the macrocyclic ligand, TACN, over a range of other nitrogen- and oxygen-containing macrocycles. Reaction of anaerobically prepared iron-TACN complexes with dioxygen gave the same product as monitored by UV/vis spectroscopy. KO2 is able to oxidize catechols with both electron-donating and electron-withdrawing substituents, implying a different mechanism for extradiol cleavage. Saturation kinetics were observed for catechols, which fit the Michaelis-Menten equation to give kcatapp = 4.8 × 10-3 s-1 for 3-(2′,3′-dihydroxyphenyl)propionic acid. The reaction was also found to proceed using monosodium catecholate in the absence of pyridine, but with different product ratios, giving insight into the acid/base chemistry of extradiol cleavage. In particular, extradiol cleavage in the presence of iron(II) shows a requirement for a proton donor, implying a role for an acidic group in the extradiol dioxygenase active site.

A unique series of dinuclear transition metal-polyradical complexes with a m-phenylenediamine spacer and their catalytic reactivity

Mukherjee, Soumen,Rentschler, Eva,Weyhermueller, Thomas,Wieghardt, Karl,Chaudhuri, Phalguni

, p. 1828 - 1829 (2003)

A series of dinuclear transition metal complexes with either six or four iminosemiquinone radicals, in which the metal centres are separated by a distance of ~6.8 A, together with their catalytic reactivity is reported.

Design of a mononuclear copper(II)-phenanthroline complex: Catechol oxidation, DNA cleavage and antitumor properties

Dey, Dhananjay,Das, Subrata,Yadav, Hare Ram,Ranjani, Anandan,Gyathri, Loganathan,Roy, Sanjay,Guin, Partha Sarathi,Dhanasekaran, Dharumadurai,Choudhury, Angshuman Roy,Akbarsha, Mohammad Abdulkader,Biswas, Bhaskar

, p. 106 - 114 (2016)

A mononuclear copper(II) complex [Cu(phen)(OH2)2(NO3)](NO3) (1) [phen = 1,10-phenanthroline] has been synthesized and structurally characterized by different spectroscopic characterization methods including sing

A family of vanadate esters of monoionized and diionized aromatic 1,2-diols: Synthesis, structure, and redox activity

Baruah, Bharat,Das, Samir,Chakravorty, Animesh

, p. 4502 - 4508 (2002)

The concerned diols (general abbreviation, H2L) are catechol (H2L1) and its 3,5-Bu2t derivative (H2L2). Esters of the type VO(xsal)(HL), 2, are obtained by reacting H2L with VO(xsal)(H2O) or VO(xsal)(OMe)(HOMe), where xsal2- is the diionized salicylaldimine of glycine (x = g), L-alanine (x = a), or L-valine (x = v). The reaction of VO(acac)2 with H2L and the salicylaldimine (Hpsal) of 2-picolylamine has furnished VO(psal)(L), 3. In the structures of VO-(gsal)(HL1), 2a, and VO(vsal)(HL2), 2f, the HL- ligand is O,O-chelated, the phenolic oxygen lying trans to the oxo oxygen atom. The xsal2- coligand has a folded structure and the conformation of 2f is exclusively endo. In both 2a and 2f the phenolic oxygen atom is strongly hydrogen bonded (O···O, 2.60 A) to a carboxylic oxygen atom of a neighboring molecule. In VO(psal)(L2)·H2O, 3b, the diionized diol is O,O-chelated to the metal and the water molecule is hydrogen bonded to a phenoxidic oxygen atom (O···O, 2.84 A). The C-O and C-C distances in the V(diol) fragment reveal that 2 is a pure catecholate and 3 is a catecholate-semiquinonate hybrid. In solution each ester gives rise to a single 51V NMR signal (no diastereoisomers), which generally shifts downfield with a decrease in the ester LMCT band energy. The V(V)/V(IV) and catecholate-semiquinonate reduction potentials lie near -0.75 and 0.35, and 1.10 and 0.70 V vs SCE for 2 and 3, respectively. Molecular oxygen reacts smoothly with 2 quantitatively furnishing the corresponding o-quinone, and in the presence of H2L the reaction becomes catalytic. In contrast, type 3 esters are inert to oxygen. The initial binding of O2 to 2 is proposed to occur via hydrogen bonding with chelated HL-.

Oxygen binding and activation by the complexes of PY2- and TPA-appended diphenylglycoluril receptors with copper and other metals

Sprakel, Vera S. I.,Feiters, Martin C.,Meyer-Klaucke, Wolfram,Klopstra, Marten,Brinksma, Jelle,Feringa, Ben L.,Karlin, Kenneth D.,Nolte, Roeland J. M.

, p. 3522 - 3534 (2005)

The copper(I) complexes of diphenylglycoluril basket receptors 1 and 2, appended with bis(2-ethylpyridine)amine (PY2) and tris(2-methylpyridine)amine (TPA), respectively, and their dioxygen adducts were studied with low-temperature UV-vis and X-ray absorption spectroscopy (XAS). The copper(I) complex of 1, [1-Cu(I)2] or 1a, forms a μ-η2:η2 dioxygen complex, whereas the copper(I) complex of 2, [2-Cu(I)2] or 2a, does not form a well defined dioxygen complex, but is oxidized to Cu(II). Dioxygen is bound irreversibly to la and the formed complex is stable over time. The coordination geometries of the above complexes were determined by XAS, which revealed that pyridyl groups and amine N-donors participate in the coordination to Cu(I) ions in the complexes of both receptors. The catalytic activities of various metal complexes of 1 and 2, that were designed as mimics of dinuclear copper enzymes that can activate dioxygen, were investigated. Phenolic substrates that were expected to undergo aromatic hydroxylation, showed oxidative polymerization without insertion of oxygen. The mechanism of this polymerization turns out to be a radical coupling reaction as was established by experiments with the model substrate 2,4-di-tert-butylphenol. In addition to Cu(II), the Mn(III) complex of 1 and the Fe(II) complex of 2 were tested as oxidation catalysts. Oxidation of catechol was observed for the Cu(II) complex of receptor 1 but the other metal complexes did not lead to oxidation. The Royal Society of Chemistry 2005.

Synthesis, crystallographic characterization and catecholase activity of a monocopper(II) and a dimanganese(III) complex with an anionic Schiff base ligand

Mitra, Merry,Maji, Ashis Kumar,Ghosh, Barindra Kumar,Kaur, Gurpreet,Choudhury, Anghsuman Roy,Lin, Chia-Her,Ribas, Joan,Ghosh, Rajarshi

, p. 15 - 19 (2013)

The mononuclear [CuII(HL)2] (1) and dinuclear [MnIII2(μ1,3-OAc)2L2] (2) [H2L = N-(2-hydroxypropyl)-3-methoxysalicylaldimine] compounds have been synthesized and charac

Dopamine polymerization promoted by a catecholase biomimetic CuII(μ-OH)CuII complex containing a triazine-based ligand

De Oliveira, José A. F.,Da Silva, Marcos P.,De Souza, Bernardo,Camargo, Tiago P.,Szpoganicz, Bruno,Neves, Ademir,Bortoluzzi, Adailton J.

, p. 15294 - 15297 (2016)

We describe herein the catecholase-like catalytic activity and dopamine polymerization by using a dinuclear [LCuII(μ-OH)2CuII](ClO4)2 (1) complex where L is the dinucleating triazine-based ligand 6-chloro-N2,N2,N4,N4-tetrakis(pyridin-2-ylmethyl)-1,3,5-triazine-2,4-diamine. The kinetic parameters (kcat = 0.318 s-1, KM = 1.6 × 10-3 mol L-1, and kcat/KM = 198.8 L s-1 mol-1), mechanistic insights into the oxidation of 3,5-di-tert-butyl catechol and early characterization of poly(dopamine) are presented.

Targeted water soluble copper-tetrazolate complexes: Interactions with biomolecules and catecholase like activities

Saha, Manideepa,Das, Mriganka,Nasani, Rajendar,Choudhuri, Indrani,Yousufuddin, Muhammed,Nayek, Hari Pada,Shaikh, Mobin M.,Pathak, Biswarup,Mukhopadhyay, Suman

, p. 20154 - 20167 (2015)

Two new mononuclear water soluble copper(ii) complexes, [Cu{(5-pyrazinyl)tetrazolate}2(1,10-phenanthroline)] 1 and [Cu{(5-pyrazinyl)tetrazolate}(1,10-phenanthroline)2](NO3)0.5(N3)0.52, have been synthesized using the metal mediated [2 + 3] cycloaddition reaction between copper bound azide and pyrazinecarbonitrile. The interactions of these copper tetrazolate complexes 1 and 2 with biomolecules like DNA and bovine serum albumin (BSA) are studied and the catecholase like catalytic activity of compound 2 is also explored. Structural determination reveals that both compounds 1 and 2 are octahedral in nature. Screening tests were conducted to quantify the binding ability of complexes (1 and 2) towards DNA and it was revealed that complex 2 has a stronger affinity to bind to CT-DNA. DFT studies indicated that a lower HOMO-LUMO energy gap between the DNA fragment and metal complexes might be the reason for this type of stronger interaction. DNA cleavage activity was explored by gel-electrophoresis and moderate to strong DNA cleavage properties were observed in the presence and absence of co-reagents. Inhibition of cleavage in the presence of sodium azide indicates the propagation of the activity through the production of singlet molecular oxygen. Furthermore enzyme kinetic studies reflect that complex 2 is also effective in mimicking catecholase like activities. An ESI-MS spectral study indicates the probable involvement of dimeric species [(phen)2Cu-(OH)2-Cu(phen)2]2+ in the catalytic cycle.

-

Barton et al.

, p. 985 (1976)

-

Copper-(I) and -(II) complexes of a macrocycle derived from 2:2 condensation of pyridine-2,6-dicarbaldehyde and 4-azaheptane-1,7-diamine; oxygenation of the copper(I) complex

Rockcliffe, David A.,Martell, Arthur E.,Reibenspies, Joseph H.

, p. 167 - 175 (1996)

A Schiff-base macrocycle was prepared by the 2:2 condensation of pyridine-2,6-dicarbaldehyde and 4-azaheptane-1, 7-diamine. It crystallized in the orthorhombic space group Fdd2 with a = 16.984(8), b = 31.322(12), c = 11.026(6) A and Z = 16. This 20-member

Catecholase activity of a copper(II) complex with a macrocyclic ligand: Unraveling catalytic mechanisms

Koval, Iryna A.,Selmeczi, Katalin,Belle, Catherine,Philouze, Christian,Saint-Aman, Eric,Gautier-Luneau, Isabelle,Schuitema, Anna Maria,Van Vliet, Marcel,Gamez, Patrick,Roubeau, Olivier,Lueken, Matthias,Krebs, Bernt,Lutz, Martin,Spek, Anthony L.,Pierre, Jean-Louis,Reedijk, Jan

, p. 6138 - 6150 (2006)

We report the structure, properties and a mechanism for the catecholase activity of a tetranuclear carbonato-bridged copper(II) cluster with the macrocyclic ligand [22]pr4pz (9,22-dipropyl-1,4,9,14,17,22,27,28,29, 30-decaazapentacyclo[22.2.1.14,7/su

SOME RULES IN TRANSFORMATIONS OF GROUP IVB o-SEMIQUINOLATES

Abakumov, G. A.,Tsaryapkin, V. A.,Gorbunova, L. V.,Cherkasov, V. K.,Razuvaev, G. A.

, p. 157 - 161 (1981)

-

Studies in the oxidative ring-opening of catechols and o-benzoquinones. Lead tetraacetate versus the copper(I) chloride/pyridine/methanol system

Walsh, James G.,Furlong, Patrick J.,Byrne, Louise A.,Gilheany, Declan G.

, p. 11519 - 11536 (1999)

Lead tetraacetate oxidative ring-opening of a series of substituted catechols provides the corresponding substituted cis, cis-2,4-diene-1,6- dioates (1-10) in fair to good yields. A number of improvements on Wiessler's procedure for this reaction are repo

Unique Copper-Organic Networks Self-Assembled from 1,3,5-Triaza-7-Phosphaadamantane and Its Oxide: Synthesis, Structural Features, and Magnetic and Catalytic Properties

?liwa, Ewelina I.,Nesterov, Dmytro S.,K?ak, Julia,Jakimowicz, Piotr,Kirillov, Alexander M.,Smoleński, Piotr

, p. 2814 - 2823 (2018)

Three new coordination compounds, namely, a zero-dimensonal dicopper(II) complex [Cu2(μ-MeCOO)4(MeOH)2](PTA = O)2 (1), a three-dimensional (3D) copper(II)-organic framework [Cu3(μ-MeCOO)6(μ3-PTA=O)]n·3.5nMeCN (2), and a mixed-valence copper(I/II) one-dimensional (1D) coordination polymer [Cu3(μ-MeCOO)4(MeCOO)(μ-PTA)2(PTA)]n (3), were self-assembled from copper(II) acetate and cage-like aminophosphine 1,3,5-triaza-7-phosphaadamantane (PTA) or its P-oxide (PTA=O). The obtained products were isolated as air-stable crystalline solids and characterized by IR and electron paramagnetic resonance spectroscopy, thermogravimetric and elemental analysis, as well as single crystal X-ray diffraction. Although all compounds bear dicopper(II) paddle-wheel tetraacetate [Cu2(μ-MeCOO)4] blocks, they are arranged into very distinct metal-organic architectures. The structure of 2 reveals an intricate 3D metal-organic framework (MOF) driven by the μ3-PTA=O spacers acting in an unusual N,N,O-tridentate mode, whereas the compound 3 discloses an infinite 1D wave-like metal-organic chain with the dicopper(II) [Cu2(μ-MeCOO)4] and monocopper(I) [Cu(PTA)(MeCOO)] blocks being interlinked by the μ-PTA linkers acting in an N,P-bidentate mode. Topological analysis of underlying nets was performed, revealing a decorated uninodal 3-connected framework with the ths topology in 2 and a uninodal 2-connected chain with the 2C1 topology in 3. Compounds 2 and 3 broaden a still very limited family of MOFs or coordination polymers assembled from PTA or its P-oxide building blocks, also showing that PTA can be applied for the generation of unusual mixed-valence copper(I/II) derivatives. Besides, 2 represents the first example of a copper-containing 3D MOF that is driven by PTA=O or any other PTA-derived block. Magnetic properties of 1-3 were investigated, modeled, and discussed in detail, resulting in the exchange coupling parameters (J = -310, -320 cm-1) that indicate a strong antiferromagnetic interaction within the dicopper(II) paddle-wheel blocks. Moreover, compounds 1 and 2 show a notable catecholase activity in the aerobic oxidation of 3,5-di-tert-butyl-catechol to 3,5-di-tert-butyl-o-benzoquinone; turnover frequency values of up to 81 min-1 were attained.

Synthesis, crystal structure and catecholase activity of a vanadium(V) Schiff base complex

Mal, Sunit Kumar,Mitra, Merry,Yadav, Hare Ram,Purohit, Chandra Shekhar,Choudhury, Angshuman Roy,Ghosh, Rajarshi

, p. 118 - 122 (2016)

An X-ray structurally characterized vanadium(V) complex, [VO2(L-H)] [L-H = H2L derived ligand (H2L = N,N′-(salicyaldimine)-1,3-diaminopropan-2-ol], was found to behave as an effective catalyst towards the oxidation of 3,5-

Zeolite framework stabilized copper complex inspired by the 2-His-1-carboxylate facial triad motif yielding oxidation catalysts

Kervinen, Kaisa,Bruijnincx, Pieter C. A.,Beale, Andrew M.,Mesu, J. Gerbrand,Van Koten, Gerard,Klein Gebbink, Robertus J. M.,Weckhuysen, Bert M.

, p. 3208 - 3217 (2006)

The stabilization of a mononuclear copper(II) complex with one MIm 2Pr ligand [MIm2Pr = 3,3-bis(1-methylimidazol-2-yl) propionate] in the supercages of zeolite Y was attempted, and the resulting materials were tested for their activi

Binuclear copper complex model of tyrosinase

Reglier,Jorand,Waegell

, p. 1752 - 1755 (1990)

-

Funabiki et al.

, p. 2760,2761, 2764 (1979)

Antibacterial and catecholase activities of Co(III) and Ni(II) Schiff base complexes

Ghosh, Ayon Kanti,Mitra, Merry,Fathima, Aafreen,Yadav, Hareram,Roy Choudhury, Angshuman,Nair, Balachandran Unni,Ghosh, Rajarshi

, p. 1 - 8 (2016)

X-ray structural analyses of two newly synthesized Schiff base-complexes, [Co(L)3] (1) and [Ni(L)2] (2) [HL = 2-((E)-(2-pyridine-2-pyridin-2-ylthio)ethylimino)methyl)phenol], reveal the bidentate chelation behavior of the ligand HL w

RUTHENIUM-CATALYZED OXIDATION OF ALCOHOLS AND CATECHOLS USING t-BUTYL HYDROPEROXIDE

Tsuji, Yasushi,Ohta, Tetsuo,Ido, Toyoyuki,Minbu, Hideshi,Watanabe, Yoshihisa

, p. 333 - 342 (1984)

Ruthenium complexes catalyze the oxidation of alcohols to the corresponding ketones or aldehydes when t-BuOOH (70percent aq.) is used as an oxidant.The reactions proceed at room temparature to give the products in excellent to fairly good yields.Among the

Mononuclear Iron(III) Complexes as Functional Models of Catechol Oxidases and Catalases

Badetti, Elena,Gjoka, Blerina,Nagy, Eszter Mrta,Bernardinelli, Grald,Kündig, Peter E.,Zonta, Cristiano,Licini, Giulia

, p. 3478 - 3484 (2015)

Mononuclear amino triphenolate iron(III) complexes have been synthesized and characterized (UV/Vis spectroscopy, cyclic voltammetry, ESI-MS, 1H NMR spectroscopy, X-ray diffraction). These complexes act as biomimetic catalysts promoting the aero

A chromophore-supported structural and functional model of dinuclear copper enzymes, for facilitating mechanism of action studies

Chen, Qiu-Cheng,Fridman, Natalia,Gross, Zeev,Tumanskii, Boris

, p. 12445 - 12450 (2021/10/08)

Type III dicopper centres are the heart of the reactive sites of enzymes that catalyze the oxidation of catechols. Numerous synthetic model complexes have been prepared to uncover the fundamental chemistry involved in these processes, but progress is still lagging much behind that for heme enzymes. One reason is that the latter gain very much from the informative spectroscopic features of their porphyrin-based metal-chelating ligand. We now introduce sapphyrin-chelated dicopper complexes and show that they may be isolated in different oxidation states and coordination geometries, with distinctive colors and electronic spectra due to the heme-like ligands. The dicopper(i) complex1-Cu2was characterized by1H and19F NMR spectroscopy of the metal-chelating sapphyrin, the oxygenated dicopper(ii) complex1-Cu2O2by EPR, and crystallographic data was obtained for the tetracopper(ii)-bis-sapphyrin complex[1-Cu2O2]2. This uncovered a non-heme [Cu4(OH)4]4?cluster, held together with the aid of two sapphyrin ligands, with structural features reminiscent of those of catechol oxidase. Biomimetic activity was demonstrated by the1-Cu2O2catalyzed aerobic oxidation of catechol to quinone; the sapphyrin ligand aided very much in gaining information about reactive intermediates and the rate-limiting step of the reaction.

Vanadium aminophenolates in catechol oxidation: Conformity with Finke's common catalyst hypothesis

Salonen, Pasi,Savela, Risto,Peuronen, Anssi,Lehtonen, Ari

supporting information, p. 6088 - 6099 (2021/05/19)

Six known aminophenolate vanadium complexes V1-V6 were examined in 3,5-di-tert-butylcatechol (1, 3,5-DTBC) oxidation. From the complexes V1-V5 have been previously shown to demonstrate catechol oxidase (catecholase) like behavior, catalytically oxidizing 1 to 3,5-di-tert-butyl-1,2-benzoquinone (2, 3,5-DTBQ). A critical re-evaluation of V1-V5, including V6 not assessed earlier, in the aerobic oxidation of 1 has revealed that several catechol dioxygenase products are obtained in addition to 2, which is produced partly by autoxidation. Mechanistic investigations into the V1-V6 catalyzed oxidation of 1 by EPR, negative mode ESI-MS and 51V NMR, in addition to semi-quantitative product distribution analyses with GC and column chromatography afford compelling evidence in support of the "common catalyst hypothesis"earlier proposed by Finke and co-workers. During the reaction, V1-V6 are partially converted in situ by H2O2 assisted leaching to vanadium catecholate complexes [V(3,5-DTBC)2(3,5-DTBSQ)] and [VO(3,5-DTBC)(3,5-DTBSQ)], where 3,5-DTBSQ = 3,5-di-tert-butyl-1,2-semiquinone, the latter of which has been implicated as the common true active catalyst in catechol dioxygenation as per the common catalyst hypothesis. The results herein suggest that vanadium aminophenolate complexes are sensitive to H2O2 mediated leaching in the presence of strong σ and π donating ligands such as 1 and 2. Furthermore, based on these results, the use of vanadium aminophenolate complexes as catechol oxidase mimics is not as warranted as previously understood.

Study of the Oxidative Cleavage Proposed in the Biogenesis of Transtaganolides/Basiliolides: Pyran-2-one Aromaticity-Mediated Regioselective Control and Biogenetic Implications

álvarez, José María,Jorge, Zacarías D.,Massanet, Guillermo M.

, (2020/03/05)

The synthetic feasibility of the oxidative cleavage: epoxidation of 7-O-geranylscopoletin followed by electrocyclic ring-opening, proposed in the biogenesis of transtaganolides/basiliolides is studied. Unlike the proposed pericyclic reactions, this pathway has not yet been addressed. Three synthetic strategies have been tested consisting of: i) Baeyer–Villiger oxidation of p-quinoids, ii) hydrolysis of quinone monoketals, or iii) direct fragmentation by using oxygen donors. Oxidation of the benzene ring of hydroxylated coumarins has been achieved using peroxyacids, but cleavage took place between undesired positions. The aromaticity conservation of the pyran-2-one cycle during oxidation is the controlling factor of these observed regioselectivities. The use of a 4,5-dihydroxy-2-methoxycinnamate model, in which the pyran-2-one ring does not exert influence on oxidation, has allowed the design of a synthetic sequence toward an analogue of the natural pyran-2-one isolated from Thapsia transtagana, key in the biogenesis. Mechanistic proposals for the obtained results as well as their biogenetic implications are raised.

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