Environmentally Benign Oxidants

Strukul, Giorgio; Scarso, Alessandro

doi:10.1002/9781118356760.ch1

Cited by 29 publications

(29 citation statements)

References 67 publications

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“…The use of H2O2 is recommended due to its highly environmentally acceptable character [30] and involves the nucleophilic attack of HOO − generated in situ to the electron-poor C=C double bond. Initially the epoxides were synthesized in the racemic form from the VBPs shown in Scheme 1, using NaOH as the base to provide suitable amounts of material to perform the enantiomer separation, using chiral HPLC for the subsequent ee evaluation.…”

Section: Resultsmentioning

confidence: 99%

Organocatalytic Stereoselective Epoxidation of Aryl-Substituted Vinylidenebisphosphonate Esters: On the Way to Chiral Anti-Osteoporosis Drugs

Chiminazzo¹,

Sperni²,

Scarso³

et al. 2017

Preprint

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Abstract:The synthesis of a new class of epoxide derivatives from prochiral vinylidene bisphosphonate (VBP) precursors is reported using hydrogen peroxide as the terminal oxidant. The reaction is carried out using a series of possible organic activators having a basic character, with the best results being observed using quinine and sparteine. These activators not only provide from good to excellent epoxide yields with a large variety of VBPs, but also interesting enantioselectivities in the 67%-96% ee range, at least in the case of the Ph and m-MeO-Ph VBP derivatives, opening the way to a number of chiral anti-osteoporosis potentially active pharmaceutical ingredients.

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Section: Resultsmentioning

confidence: 99%

Organocatalytic Stereoselective Epoxidation of Aryl-Substituted Vinylidenebisphosphonate Esters: On the Way to Chiral Anti-Osteoporosis Drugs

Chiminazzo¹,

Sperni²,

Scarso³

et al. 2017

Preprint

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“…The catalytic systems are based on any of the above Cu(I) 1 or Cu(II) 2 or 3 complexes, hydrogen peroxide (30% aqueous solution) as the oxidizing agent, at room temperature (r.t.), in the absence of added solvent or additives. The use of other environmentally benign [34] peroxidative oxidants, such as tert -butyl hydroperoxide (TBHP, 70% aqueous solution), was also considered.…”

Section: Resultsmentioning

confidence: 99%

“…The development of more efficient catalysts, under milder conditions, at room temperature and using low toxicity media and oxidizing agents is needed [18,19,20,21,27,28,29,30,31,32,33,34]. Hydrogen peroxide is one of the best options in this regard since H 2 O is the sole by-product and exhibits an atom efficiency and e-factor similar to dioxygen [34]. Thus, peroxidative (with H 2 O 2 ) alkane oxidations were the selected reactions for the present study.…”

Section: Introductionmentioning

confidence: 99%

Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyl)tetrazolate Metal-Organic Frameworks

et al. 2015

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Microwave assisted synthesis of the Cu(I) compound ]n [1, 4-ptz = 5-(4-pyridyl)tetrazolate] has been performed by employing a relatively easy method and within a shorter period of time compared to its sister compounds. The syntheses of the Cu(II) compounds [Cu3(µ3-4-ptz)4(µ2-N3)2(DMF)2]n·(DMF)2n (2) and [Cu(µ2-4-ptz)2(H2O)2]n (3) using a similar method were reported previously by us. MOFs 1-3 revealed high catalytic activity toward oxidation of cyclic alkanes (cyclopentane, -hexane and -octane) with aqueous hydrogen peroxide, under very mild conditions (at room temperature), without any added solvent or additive. The most efficient system (2/H2O2) showed, for the oxidation of cyclohexane, a turnover number (TON) of 396 (TOF of 40 h −1 ), with an overall product yield (cyclohexanol and cyclohexanone) of 40% relative to the substrate. Moreover, the heterogeneous catalytic OPEN ACCESSMolecules 2015, 20 19204 systems 1-3 allowed an easy catalyst recovery and reuse, at least for four consecutive cycles, maintaining ca. 90% of the initial high activity and concomitant high selectivity.

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“…The development and implementation of greener and more sustainable catalytic epoxidation processes using environmentally benign oxidants is a challenging goal in modern organic syntheses. Hydrogen peroxide is, along with molecular oxygen, the most sought-after oxidant in terms of environmental sustainability because it produces water as its only byproduct [4][5][6].…”

Section: Introductionmentioning

confidence: 99%

Cyclohexene Oxidation with H2O2 over Metal-Organic Framework MIL-125(Ti): The Effect of Protons on Reactivity

et al. 2019

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The catalytic performance of the titanium-based metal–organic framework MIL-125 was evaluated in the selective oxidation of cyclohexene (CyH) with environmentally friendly oxidants, H2O2 and tBuOOH. The catalytic activity of MIL-125 as well as the oxidant utilization efficiency and selectivity toward epoxide and epoxide-derived products can be greatly improved by acid additives (HClO4 or CF3SO3H). In the presence of 1 molar equivalent (relative to Ti) of a proton source, the total selectivity toward CyH epoxide and trans-cyclohexane-1,2-diol reached 75–80% at 38–43% alkene conversion after 45 min of reaction with 1 equivalent of 30% H2O2 at 50 °C. With 50% H2O2 as the oxidant, the total selectivity toward heterolytic oxidation products increased up to 92% at the same level of alkene conversion. N2 adsorption, powder X-ray diffraction (PXRD), and infrared (IR) spectroscopy studies before and after the catalytic oxidations confirmed the absence of structural changes in the Metal–organic framework (MOF) structure. MIL-125 was stable toward titanium leaching, behaved as a truly heterogeneous catalyst, and could easily be recovered and reused several times without any loss of the catalytic properties.

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Environmentally Benign Oxidants

Cited by 29 publications

References 67 publications

Organocatalytic Stereoselective Epoxidation of Aryl-Substituted Vinylidenebisphosphonate Esters: On the Way to Chiral Anti-Osteoporosis Drugs

Organocatalytic Stereoselective Epoxidation of Aryl-Substituted Vinylidenebisphosphonate Esters: On the Way to Chiral Anti-Osteoporosis Drugs

Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyl)tetrazolate Metal-Organic Frameworks

Cyclohexene Oxidation with H2O2 over Metal-Organic Framework MIL-125(Ti): The Effect of Protons on Reactivity

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