Carbon-carbon double bond cleavage using solid-supported potassium permanaganate on silica gel

Tercio, J.; Ferreira, B.; Cruz, Welington O.; Vieira, Paulo C.; Yonashiro, Massami

doi:10.1021/jo00392a041

Cited by 40 publications

(7 citation statements)

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“…Alternative procedure using KMnO 4 heterogenized onto silica gel: 33 Either meso -Tetrakis(pentafluorophenyl)-2,3-dihydroxychlorin osmate ester (0.300 g, 2.16 × 10 −4 mol) or meso -Tetrakis(pentafluorophenyl)-2,3-dihydroxychlorin 7gH 2 (0.300 g, 2.98 × 10 −4 mol) were dissolved in a 250 mL round-bottom flask equipped with a stir bar in CHCl 3 (100 mL). To the stirred porphyrinoid solution was added KMnO 4 heterogenized onto silica (5.19 g; corresponding to a ~15-fold stoichiometric excess of oxidant).…”

Section: Methodsmentioning

confidence: 99%

meso-Arylporpholactones and their Reduction Products

et al. 2012

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The rational syntheses of meso-tetraaryl-3-oxo-2-oxaporphyrins 5, known as porpholactones, via MnO 4 − mediated oxidations of the corresponding meso-tetraaryl-2,3dihydroxychlorins ( 7) is detailed. Since chlorin 7 is prepared from the parent porphyrin 1, this amounts to a 2-step replacement of a pyrrole moiety in 1 by an oxazolone moiety. The stepwise reduction of the porpholactone 5 results in the formation of chlorin analogues, meso-tetraaryl-3-hydroxy-2oxachlorin ( 11) and meso-tetraaryl-2-oxachlorins (12). The reactivity of 11 with respect to nucleophilic substitution by O-, N-, and S-nucleophiles is described. The profound photophysical consequences of the formal replacement of a pyrrole with an oxazolone (porphyrin-like chromophore) or (substituted) oxazole moiety (chlorin-like chromophore with, for the parent oxazolochlorin 12, red-shifted Q x band with enhanced oscillator strengths) are detailed and rationalized on the basis of SAC−CI and MNDO-PSDCI molecular orbital theory calculations. The single crystal X-ray structures of the porpholactones point at a minor steric interaction between the carbonyl oxygen and the flanking phenyl group. The essentially planar structures of all chromophores in all oxidation states prove that the observed optical properties originate from the intrinsic electronic properties of the chromophores and are not subject to conformational modulation.

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Section: Methodsmentioning

confidence: 99%

meso-Arylporpholactones and their Reduction Products

et al. 2012

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“…The mother liquor was concentrated, dissolved in methylene chloride (320 mL), and treated at -78 °C with boron tribromide solution (1 M in methylene chloride, 40 (40 mL) and treated with potassium permanganate (8.5 g, 5.38 mmol) adsorbed on silica gel. 46 The suspension was stirred at room temperature and then treated with Na2SO4 and filtered through silica gel. After concentration, the crude product was crystallized from ethyl acetate and n-hexane to give 6-(6-bromohexyloxy)-3-(4-bromophenyl)benzo[d]isothiazole 1,1-dioxide (25) (650 mg, 28%) and starting material 23 (1.23 (12 mL).…”

Section: Allyl[6-[3-(4-bromophenyl)benzo[d]isoxazol-6-yloxy]hexyl]met...mentioning

confidence: 99%

Synthesis and Structure−Activity Studies of Novel Orally Active Non-Terpenoic 2,3-Oxidosqualene Cyclase Inhibitors

et al. 2003

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New orally active non-terpenoic inhibitors of human 2,3-oxidosqualene cyclase (hOSC) are reported. The starting point for the optimization process was a set of compounds derived from a fungicide project, which in addition to showing high affinity for OSC from Candida albicans showed also high affinity for human OSC. Common structural elements of these inhibitors are an amine residue and an electrophilic carbonyl C atom embedded in a benzophenone system, which are at a distance of about 10.7 A. Considering that the keto moiety is in a potentially labile position, modifications of the substitution pattern at the benzophenone as well as annelated heteroaryl systems were explored. Our approach combined testing of the compounds first for increased binding affinity and for increased stability in vitro. Most promising compounds were then evaluated for their efficacy in lowering plasma total cholesterol (TC) and plasma low-density lipoprotein cholesterol (LDL-C) in hyperlipidemic hamsters. In this respect, the most promising compounds are the benzophenone derivative 1.fumarate and the benzo[d]isothiazol 24.fumarate, which lowered TC by 40% and 33%, respectively.

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“…In addition, permanganate-mediated oxidations are usually recognized as eco-friendly because the co-product formed, manganese dioxide, can be recycled. Solid supports such as molecular sieves, graphite reagent, polystyrene, alumina, silica gel and copper sulfate pentahydrate have been previously used for permanganate-based oxidation of alcohols to carbonyl compounds, sulfides to sulfones, diols to lactones, and oximes to ketones [32][33][34][35][36][37][38][39][40][41][42][43][44]. The oxidation of olefins to diketones, αhydroxy ketones and epoxides has been described with permanganate-supported on copper sulfate pentahydrate and iron(III) perchlorate hydrate [45,46].…”

Section: Accepted Manuscriptmentioning

confidence: 99%

“…This assay scores the agonist-evoked GDP/GTP exchange that occurs at the G-protein within the receptor-G protein complex, and is classically used to quantify receptor activation. Neither of the compounds acted as agonists in the [35 S]GTPγS binding assays on hMORM A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPTand hDOR (Figures 3C and 3E). Conversely they acted as antagonists of DAMGO-mediated activation of hMOR at the concentrations tested, as well as antagonists of SNC80-mediated activation of hDOR at the highest concentration of 50 µM(Figures 3D and 3F).…”

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confidence: 98%

Synthesis of 7β-hydroxy-8-ketone opioid derivatives with antagonist activity at mu- and delta-opioid receptors

Ahonen

Rinne

Grutschreiber

et al. 2018

European Journal of Medicinal Chemistry

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Despite extensive years of research, the direct oxidation of the 7,8-double bond of opioids has so far received little attention and knowledge about the effects of this modification on activity at the different opioid receptors is scarce. We herein report that potassium permanganate supported on iron(II) sulfate heptahydrate can be used as a convenient oxidant in the one-step, heterogeneous conversion of Δ-opioids to the corresponding 7β-hydroxy-8-ketones. Details of the reaction mechanism are given and the effects of the substituent at position 6 of several opioids on the reaction outcome is discussed. The opioid hydroxy ketones prepared are antagonists at the mu- and delta-opioid receptors. Docking simulations and detailed structure-activity analysis revealed that the presence of the 7β-hydroxy-8-ketone functionality in the prepared compounds can be used to gain activity towards the delta opioid receptor. The 7β-hydroxy-8-ketones prepared with this method can also be regarded as versatile intermediates for the synthesis of other opioids of interest.

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Carbon-carbon double bond cleavage using solid-supported potassium permanaganate on silica gel

Cited by 40 publications

References 0 publications

meso-Arylporpholactones and their Reduction Products

meso-Arylporpholactones and their Reduction Products

Synthesis and Structure−Activity Studies of Novel Orally Active Non-Terpenoic 2,3-Oxidosqualene Cyclase Inhibitors

Synthesis of 7β-hydroxy-8-ketone opioid derivatives with antagonist activity at mu- and delta-opioid receptors

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