Catalytic, regioselective, and green methods for rearrangement of 1,2-diaryl epoxides to carbonyl compounds employing metallic triflates, Brønsted-acidic ionic liquids (ILs), and IL/microwave; experimental and computational substituent effect study on aryl versus hydrogen migration

Jamalian, Arezu; Rathman, Benjamin M.; Borosky, Gabriela L.; Laali, Kenneth K.

doi:10.1016/j.apcata.2014.08.009

Cited by 17 publications

(8 citation statements)

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“…As a mixture of stereoisomers would eventually result in an atactic polyamide, we were interested in a stereoselective catalysis which would enable the synthesis of the pure isomers-but complex 51,52 and costly [53][54][55][56] catalysts should be avoided. We assumed that a concerted mechanism leads to inversion of the methyl group, whereas an ionic two-step mechanism results in a mixture 53,[57][58][59] . After screening for optimized reaction conditions (Supplementary Tables 2-8) with respect to solvent polarity, concentrations of reactants, and temperatures, we identified several trends: (I) with decreasing polarity of the solvent, inversion of the methyl group to isomer 3-3S is preferred; (II) increasing substrate concentration leads to formation of high-boiling molecules, presumably oligomers; (III) oligomer formation decreases at higher temperatures; (IV) various side products are formed under aqueous acidic conditions; and (V) very acidic conditions under exclusion of water are most promising.…”

Section: Resultsmentioning

confidence: 99%

Biobased chiral semi-crystalline or amorphous high-performance polyamides and their scalable stereoselective synthesis

et al. 2020

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The use of renewable feedstock is one of the twelve key principles of sustainable chemistry. Unfortunately, bio-based compounds often suffer from high production cost and low performance. To fully tap the potential of natural compounds it is important to utilize their functionalities that could make them superior compared to fossil-based resources. Here we show the conversion of (+)-3-carene, a by-product of the cellulose industry into ε-lactams from which polyamides. The lactams are selectively prepared in two diastereomeric configurations, leading to semi-crystalline or amorphous, transparent polymers that can compete with the thermal properties of commercial high-performance polyamides. Copolyamides with caprolactam and laurolactam exhibit an increased glass transition and amorphicity compared to the homopolyamides, potentially broadening the scope of standard polyamides. A fourstep one-vessel monomer synthesis, applying chemo-enzymatic catalysis for the initial oxidation step, is established. The great potential of the polyamides is outlined.

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Section: Resultsmentioning

confidence: 99%

Biobased chiral semi-crystalline or amorphous high-performance polyamides and their scalable stereoselective synthesis

et al. 2020

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“…In another recent work efficient and selective rearrangements of stilbene epoxides were observed with 0.1–0.3 equiv of [(HSO 3 ) 4 C 4 C 1 im][OTf] in dichloromethane as shown in Figure . A substituent effect study was performed with a series of singly substituted 1,2-diphenyl oxiranes and competing formation of ketones was observed in acidic ionic liquids …”

Section: Applications Of Acidic Ionic Liquidsmentioning

confidence: 99%

Acidic Ionic Liquids

2016

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Ionic liquid with acidic properties is an important branch in the wide ionic liquid field and the aim of this article is to cover all aspects of these acidic ionic liquids, especially focusing on the developments in the last four years. The structural diversity and synthesis of acidic ionic liquids are discussed in the introduction sections of this review. In addition, an unambiguous classification system for various types of acidic ionic liquids is presented in the introduction. The physical properties including acidity, thermo-physical properties, ionic conductivity, spectroscopy, and computational studies on acidic ionic liquids are covered in the next sections. The final section provides a comprehensive review on applications of acidic ionic liquids in a wide array of fields including catalysis, CO2 fixation, ionogel, electrolyte, fuel-cell, membrane, biomass processing, biodiesel synthesis, desulfurization of gasoline/diesel, metal processing, and metal electrodeposition.

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“…Among them, protic acidic ionic liquids (AILs) have been extensively utilized as catalysts and reagents in organic synthesis [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. This class of ionic liquids combine the advantages of both liquid and solid acids.…”

Section: Introductionmentioning

confidence: 99%

Design, characterization, and use of N,N-diethyl-N-sulfoethanaminium hydrogen sulfate {[Et3N-SO3H]HSO4} as a novel and highly efficient catalyst for preparation of α,α′-bis(arylidene)cycloalkanones

et al. 2016

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The aim of this work is to introduce a novel and attractive protic acidic ionic liquid as catalyst for organic synthesis. To achieve this aim, N,N-diethyl-N-sulfoethanaminium hydrogen sulfate {[Et 3 N-SO 3 H]HSO 4 } was prepared by reaction of NEt 3 with ClSO 3 H and then with H 2 SO 4 . The novel acidic ionic liquid was identified by Fourier-transform infrared (FT-IR), 1 H nuclear magnetic resonance (NMR), 13 C NMR, and mass spectroscopies. Its catalytic activity was then examined in the cross-aldol condensation reaction of arylaldehydes with cycloalkanones under solvent-free conditions, obtaining a,a 0 -bis(arylidene)cycloalkanones in high yield after short reaction time. Graphical AbstractKeywords Protic acidic ionic liquid Á N,N-Diethyl-N-sulfoethanaminium hydrogen sulfate {[Et 3 N-SO 3 H]HSO 4 } Á a,a 0 -Bis(arylidene)cycloalkanone Á Crossaldol condensation Á Solvent-free & Abdolkarim Zare

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Catalytic, regioselective, and green methods for rearrangement of 1,2-diaryl epoxides to carbonyl compounds employing metallic triflates, Brønsted-acidic ionic liquids (ILs), and IL/microwave; experimental and computational substituent effect study on aryl versus hydrogen migration

Cited by 17 publications

References 48 publications

Biobased chiral semi-crystalline or amorphous high-performance polyamides and their scalable stereoselective synthesis

Biobased chiral semi-crystalline or amorphous high-performance polyamides and their scalable stereoselective synthesis

Acidic Ionic Liquids

Design, characterization, and use of N,N-diethyl-N-sulfoethanaminium hydrogen sulfate {[Et3N-SO3H]HSO4} as a novel and highly efficient catalyst for preparation of α,α′-bis(arylidene)cycloalkanones

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