(1R,3R)-2-Methylene-1,3-dithiolane 1,3-dioxide: a highly reactive and highly selective chiral ketene equivalent in cycloaddition reactions with a broad range of dienes

Aggarwal, Varinder K.; Gültekin, Zeynep; Grainger, Richard S.; Adams, Harry; Spargo, Peter L.

doi:10.1039/a804607g

Cited by 58 publications

(41 citation statements)

References 32 publications

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“…The preparation and handling of air‐sensitive materials were carried out in a N 2 drybox (MBraun ULK 1000) with O 2 and H 2 O concentrations of <1 ppm. Commercially available 70 % meta ‐chloroperbenzoic acid was purified prior to use by following a reported procedure 42. The deuterated substrate [D 4 ]‐9,10‐dihydroanthracene was prepared from 9,10‐dihydroanthracene by following previously reported procedures 43…”

Section: Methodsmentioning

confidence: 99%

Reactivity of a Nickel(II) Bis(amidate) Complex withmeta‐Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species

Corona

Pfaff

Acuña‐Parés

et al. 2015

Chemistry A European J

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Herein, we report the formation of a highly reactive nickel-oxygen species that has been trapped following reaction of a Ni(II) precursor bearing a macrocyclic bis(amidate) ligand with meta-chloroperbenzoic acid (HmCPBA). This compound is only detectable at temperatures below 250 K and is much more reactive toward organic substrates (i.e., C-H bonds, C=C bonds, and sulfides) than previously reported well-defined nickel-oxygen species. Remarkably, this species is formed by heterolytic O-O bond cleavage of a Ni-HmCPBA precursor, which is concluded from experimental and computational data. On the basis of spectroscopy and DFT calculations, this reactive species is proposed to be a Ni(III) -oxyl compound.

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Section: Methodsmentioning

confidence: 99%

Reactivity of a Nickel(II) Bis(amidate) Complex withmeta‐Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species

Corona

Pfaff

Acuña‐Parés

et al. 2015

Chemistry A European J

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“…Metachloroperoxybenzoic acid (mCPBA) was purchased (Sigma-Aldrich) and contained a maximum purity of 77% peracid. To obtain 99% mCPBA, the purchased compound was purified using previously described methods; because the highly purified mCPBA is an explosive hazard if heated, the temperature was carefully controlled [39]. The mCPBA purity was determined using the triiodide assay (e353 = 25.5 mM -1 .cm -1 ) [40].…”

Section: Methodsmentioning

confidence: 99%

Reaction of ferricCaldariomyces fumagochloroperoxidase withmeta-chloroperoxybenzoic acid: sequential formation of compound I, compound II and regeneration of the ferric state using one reactant

Collins

Isaac

Coulter

et al. 2013

J. Porphyrins Phthalocyanines

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The mechanism of the reaction between ferric Caldariomyces fumago chloroperoxidase (CCPO) and meta-chloroperoxybenzoic acid (mCPBA) has been examined. It has previously been established that an Fe(IV)-oxo porphyrin radical species known as Compound I (Cpd I) is formed by two-electron oxidation of the native ferric enzyme by a variety of oxidants including organic peracids and hydroperoxides. Cpd I can return to the ferric state either by direct oxygen insertion into an organic substrate (e.g. a P450 oxygenase-like reaction), or by two consecutive one-electron additions, the first resulting in an intermediate Fe(IV)-oxo species known as Compound II (Cpd II). There has been much debate over the role of Cpd II and the details of its structure. In the present study, both CCPO Fe(IV)-oxo intermediates are formed, but unlike most CCPO reactions, Cpd I and Cpd II are formed using the same reactant, mCPBA. Thus, the peracid is used as an oxo donor to produce Cpd I and then as a reductant to reduce Cpd I to Cpd II, and finally, Cpd II to the ferric state. The observation of saturation kinetics with respect to mCPBA concentration for each step is consistent with the formation of CCPOmCPBA complexes in each phase of the reaction. The original reaction mechanism for ferric CCPO with mCPBA was hypothesized to involve a scrambling mechanism with a unique Fe-OOO-C(O)R intermediate formed with no observed Cpd II intermediate. The data reported herein clearly demonstrate the formation of Cpd II in returning the oxidized enzyme back to its native ferric state.

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“…m-Chloro perbenzoic acid (≤77% c.p.) was purchased from Sigma-Aldrich; purified by known methods (Aggarwal et al, 1998), and used for assays. Other shunting agents, cumene hydro-peroxide (CHP), sodium periodate (NaIO 4 ), and sodium hypochlorite (bleach) were used as received.…”

Section: Methodsmentioning

confidence: 99%

Identification of Camphor Oxidation and Reduction Products in Pseudomonas putida: New Activity of the Cytochrome P450cam System

2011

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P450 enzymes are known for catalyzing hydroxylation reactions of non-activated C-H bonds. For example, P450(cam) from Pseudomonas putida oxidizes (1R)-(+)-camphor to 5-exo-hydroxy camphor and further to 5-ketocamphor. This hydroxylation reaction proceeds via a catalytic cycle in which the reduction of dioxygen (O(2)) is coupled to the oxidation of the substrate. We have observed that under conditions of low oxygen, P. putida and isolated P450(cam) reduce camphor to borneol. We characterized the formation of borneol under conditions of low oxygen or when the catalytic cycle is shunted by artificial oxidants like m-chloro perbenzoic acid, cumene hydroperoxide, etc. We also tested the toxicity of camphor and borneol with P. putida and Escherichia coli. We have found that in P. putida borneol is less toxic than camphor, whereas in E. coli borneol is more toxic than camphor. We discuss a potental ecological advantage of the camphor reduction reaction for P. putida.

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(1R,3R)-2-Methylene-1,3-dithiolane 1,3-dioxide: a highly reactive and highly selective chiral ketene equivalent in cycloaddition reactions with a broad range of dienes

Cited by 58 publications

References 32 publications

Reactivity of a Nickel(II) Bis(amidate) Complex withmeta‐Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species

Reactivity of a Nickel(II) Bis(amidate) Complex withmeta‐Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species

Reaction of ferricCaldariomyces fumagochloroperoxidase withmeta-chloroperoxybenzoic acid: sequential formation of compound I, compound II and regeneration of the ferric state using one reactant

Identification of Camphor Oxidation and Reduction Products in Pseudomonas putida: New Activity of the Cytochrome P450cam System

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