A recyclable Mn–porphyrin catalyst for enantioselective epoxidation of unfunctionalized olefins using molecular dioxygen

Farokhi, Afsaneh; Hosseini‐Monfared, Hassan

doi:10.1039/c6nj00808a

Cited by 71 publications

(33 citation statements)

References 81 publications

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“…[16,[19][20][21][22][23][24][25] Nowadays, magnetite nanoparticles are of particular interest because of their unique properties including high surface area, low toxicity, ability to be separated and biocompatibility. [16,[26][27][28][29][30] Magnetic separation renders the recycling of catalysts from solution using external magnetic fields much easier than filtration and centrifugation. In continuation of our previous investigation of catalytic activity of Schiff base complexes, [6,[9][10][11]15,19] herein we report the anchoring of novel cisdioxomolybdenum(VI) macrocyclic Schiff base complex by reaction of 1,4-bis(2-carboxyaldehydephenoxy)butane, MoO 2 Cl 2 (DMF) 2 and amino-modified magnetite nanoparticles (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Excellent alkene epoxidation catalytic activity of macrocyclic‐based complex of dioxo‐Mo(VI) on supermagnetic separable nanocatalyst

Payami

Bezaatpour

Eskandari

2017

Applied Organom Chemis

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A phenoxybutane-based Schiff base complex of cis-dioxo-Mo(VI) was supported on paramagnetic nanoparticles and characterized using powder Xray diffraction, infrared, diffuse reflectance and atomic absorption spectroscopies, scanning and transmission electron microscopies and vibrating sample magnetometry. The separable nanocatalyst was tested for the selective epoxidation of cyclohexene, cyclooctene, styrene, indene, α-pinene, 1-octene, 1-heptene, 1-dodecene and trans-stilbene using tert-butyl hydroperoxide (80% in di-tert-butyl peroxide-water, 3:2) as oxidant in chloroform. The catalyst was efficient for oxidation of cyclooctene with 100% selectivity for epoxidation with 98% conversion in 10 min. We were able to separate magnetically the nanocatalyst using an external magnetic field and used the catalyst at least six successive times without significant decrease in conversion.The turnover frequency of the catalyst was remarkable (2556 h −1 for cyclooctene). The proposed nanomagnetic catalyst has advantages in terms of catalytic activity, selectivity, catalytic reaction time and reusability by easy separation.

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Section: Introductionmentioning

confidence: 99%

Excellent alkene epoxidation catalytic activity of macrocyclic‐based complex of dioxo‐Mo(VI) on supermagnetic separable nanocatalyst

Payami

Bezaatpour

Eskandari

2017

Applied Organom Chemis

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“…Also, the polarity, low coordinating ability and aprotic nature of acetonitrile are play the main role in improving the activity of the catalyst . Besides, it seems that polar solvents have a significant effect on the activation of intermediate species in manganese–porphyrin compounds and increase their catalytic activity . In fact, organic polar solvents, such as CH 3 CN, could affect access of substrate to active sites by increasing the solubility and diffusion of reactants in ILs …”

Section: Resultsmentioning

confidence: 99%

“…Oxygenation of the olefin seems to occur via a reactive high‐valent Mn–oxo intermediate, which is produced by the reaction of the peroxyacid with the Mn–porphyrin of p(APTMACl)‐[Mn(TPPS)(OAc)]. The high‐valent Mn–oxo intermediate then reacts with the olefin to generate the epoxide (as shown in Scheme ) …”

Section: Resultsmentioning

confidence: 99%

Polymeric ionic liquid material‐anchored Mn–porphyrin anion: Heterogeneous catalyst for aerobic oxidation of olefins

Yazdely

Ghorbanloo

Hosseini‐Monfared

2018

Applied Organom Chemis

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P(APTMACl)‐[Mn(TPPS)(OAc)] heterogeneous catalyst system comprised of anionic [Mn(tetrakis(4‐sulfonatophenyl)porphyrin)(OAc)] ([Mn(TPPS)(OAc)]) embedded within cationic cross‐linked polymeric ionic liquid (poly[(3‐acrylamidopropyl)trimethylammonium chloride], p(APTMACl)) hydrogel matrices was used for the selective aerobic oxidation of olefins. P(APTMACl)‐[Mn(TPPS)(OAc)] hydrogel was synthesized by radical polymerization in a solution of cationic APTMACl as an ionic liquid monomer, N,N′‐methylenebisacrylamide as cross‐linking agent, ammonium persulfate as initiator and N,N,N′,N′‐tetramethylmethylenediamine as accelerator in the presence of anionic [Mn(TPPS)(OAc)]. P(APTMACl)‐[Mn(TPPS)(OAc)] was characterized using Fourier transform infrared, diffuse reflectance UV–visible and atomic absorption spectroscopies and scanning electron microscopy. Differential scanning calorimetry was used for measuring the glass transition temperature. Catalytic activity of p(APTMACl)‐[Mn(TPPS)(OAc)] was investigated in the aerobic oxidation of olefins with emphasis on the effect of various parameters such as temperature, catalyst amount, substituent effect, etc. The catalyst was easily recovered from the reaction medium and could be re‐used for another seven runs without significant loss of activity.

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“…34 In the same year, Paul Le Maux et al reported an enantioselective water soluble iron porphyrin as catalyst for the asymmetric epoxidation of alkenes with iodobenzene diacetate as an oxidant. 38 In the same year, we reported asymmetric epoxidation of styrene and its derivatives, which were catalyzed by insitu metal complexes of chiral porphyrin ligands. 36 In the year 2015, Wen Dai et al reported porphyrin inspired iron catalyst for the asymmetric epoxidation of electron defecient olefins.…”

Section: Introductionmentioning

confidence: 99%

Chiral porphyrin imine manganese complex as catalyst for asymmetric epoxidation of styrene derivatives

Ananthi

Enoch

2019

Chirality

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New chiral porphyrin imine was synthesized from (S)-3-benzyl-2-methyl-4phenylbutanal according to dipyrromethane method using trifluoroacetic acid, BF 3 etherate, and p-chloranil. Manganese complex of this chiral porphyrin imine ligand was used as catalyst in the asymmetric epoxidation of styrene derivatives possessing different substituents. Styrene derivatives possessing electron withdrawing groups gave the corresponding chiral epoxides in high yield up to 98% and ee up to 99%. The mechanism for the catalytic asymmetric epoxidation was also discussed based on transfer of oxygen.KEYWORDS asymmetric epoxidation, asymmetric synthesis, chiral epoxides, chiral porphyrin manganese complexes, epoxidation of styrene

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A recyclable Mn–porphyrin catalyst for enantioselective epoxidation of unfunctionalized olefins using molecular dioxygen

Abstract: A highly efficient green process for the asymmetric epoxidation of olefins by an easy to synthesise Mn–porphyrin and O2/aldehyde is reported.

Cited by 71 publications

References 81 publications

Excellent alkene epoxidation catalytic activity of macrocyclic‐based complex of dioxo‐Mo(VI) on supermagnetic separable nanocatalyst

Excellent alkene epoxidation catalytic activity of macrocyclic‐based complex of dioxo‐Mo(VI) on supermagnetic separable nanocatalyst

Polymeric ionic liquid material‐anchored Mn–porphyrin anion: Heterogeneous catalyst for aerobic oxidation of olefins

Chiral porphyrin imine manganese complex as catalyst for asymmetric epoxidation of styrene derivatives

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