Silyl peroxides as effective oxidants in the Baeyer–Villiger reaction with chloroaluminate(III) ionic liquids as catalysts

Baj, Stefan; Słupska, Roksana; Chrobok, Anna; Drożdż, Agnieszka

doi:10.1016/j.molcata.2013.04.023

Cited by 17 publications

(17 citation statements)

References 20 publications

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“…Zr(OTf) 4 and W(OTf) 6 were synthesized according to reported methods. Zr(OTf) 4 and W(OTf) 6 were synthesized according to reported methods.…”

Section: Experimental Section Materialsmentioning

confidence: 99%

“…[4] Subsequently they reportedt hat relatively high yields (89-94%)o fl actonesc an be achieved in 1-120min at room temperature with H 2 O 2 as the oxidant in 1:3[ C 4 MIM]Cl/ GaCl 3 (X GaCl 3 = 0.75) Lewis acidic ionic liquid. Baeyer-Villigero xidation of cyclic ketones plays an important role in the synthesis of lactones (Scheme 1).…”

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confidence: 99%

“…However,n og-lactones werep roduced. [4,13] In particular, imidazoliumbased ionic liquids have been extensively studied recently. [11] Moreover,m acrolides have seldom been reported as the startingm aterials to synthesize g-lactones, with the notable exception of as tudy by Dumesic and co-workers,w ho reported the conversion of d-valerolactone and e-caprolactone into g-lactones over SiO 2 /Al 2 O 3 with 40 %a nd 23 %p roduct selectivity,respectively.…”

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confidence: 99%

“…Chrobok and co-workers describedt he oxidation of cyclic ketonest o g-lactones in 97 %y ield with silyl peroxides in the presence of 1:2[ HMIM][Cl]/AlCl 3 (X AlCl 3 ¼0:67 ,a cidic)i onic liquids. [4] Subsequently they reportedt hat relatively high yields (89-94%)o fl actonesc an be achieved in 1-120min at room temperature with H 2 O 2 as the oxidant in 1:3[ C 4 MIM]Cl/ GaCl 3 (X GaCl 3 = 0.75) Lewis acidic ionic liquid. [5] The Baeyer-Villiger oxidation step is simple andt he atom economyi shigh.…”

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confidence: 99%

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W(OTf)₆‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid

Xie

Deng

2018

ChemSusChem

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γ-Lactones are an important class of fine chemical products and are widely used in perfumes, medicines, pesticides, dyes, and other fields. Herein, a new method for γ-lactones preparation based on ring contraction was developed. Starting from macrolides, W(OTf) was used to catalyze the ring-opening polymerization then depolymerization. The depolymerization step was not a common ring-closing process, and the carbon number of the ring was reduced one by one by rearrangement to form the most thermodynamically stable five-membered ring compounds. γ-Caprolactone (180 °C for 10 h) was obtained in a yield of 94 % when [EMIM]OTf was used as the solvent, and the yield of isolated product was up to 85 %. The interaction of various components and the reaction mechanism were studied by FTIR spectroscopy and H NMR spectroscopy, respectively. Furthermore, γ-lactones could be produced when the substrate was extended to terminal hydroxyfatty acids. Unexpectedly, the catalyst was poisoned by 1 equivalent of H O added during the process and thus the yield decreased greatly. The reaction is green and simple, and proceeds in one pot with high atom economy (100 % for macrolides and with water as the only byproduct for terminal hydroxyfatty acid), which provides a promising approach to synthesizing γ-lactones.

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“…Zr(OTf) 4 and W(OTf) 6 were synthesized according to reported methods. Zr(OTf) 4 and W(OTf) 6 were synthesized according to reported methods.…”

Section: Experimental Section Materialsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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W(OTf)₆‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid

Xie

Deng

2018

ChemSusChem

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“…In the early stage, researchers only concerned the electrochemical properties of chloroaluminate ILs [2][3][4]. Nowadays, owing to the strong Lewis acidity of chloroaluminate ILs, the research focus has been switched to their applications as catalysts for varies of organic reactions, such as alkylation, dealkylation, isomerization, dimerization, oligomerization, polymerization, catalytic cracking, FriedelCrafts reaction and Baeyer-Villiger reaction [5][6][7][8][9][10][11][12]. In addition, the applications in extraction, desulfurization and nanomaterial synthesis also attract chemists' interests due to their unique properties [13][14][15].…”

Section: Introductionmentioning

confidence: 99%

Theoretical study on the structure and cation–anion interaction of triethylammonium chloroaluminate ionic liquid

Liu

Wang

et al. 2015

Computational and Theoretical Chemistry

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Enantioselective Synthesis of Cyclopropanone Equivalents and Application to the Formation of Chiral β‐Lactams

et al. 2020

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Cyclopropanone derivatives have long been considered unsustainable synthetic intermediates because of their extreme strain and kinetic instability.R eported here is the enantioselective synthesis of 1-sulfonylcyclopropanols,a ss table yet powerful equivalents of the corresponding cyclopropanone derivatives,bya-hydroxylation of sulfonylcyclopropanes using ab is(silyl) peroxide as the electrophilic oxygen source. This work constitutes the first general approach to enantioenriched cyclopropanone derivatives.B oth the electronic and steric nature of the sulfonyl moiety,w hich serves as ab aselabile protecting group and confers crystallinity to these cyclopropanone precursors,w ere found to have ac rucial impact on the rate of equilibration to the corresponding cyclopropanone.T he utility of these cyclopropanone surrogates is demonstrated in amild and stereospecific formal [3+ +1] cycloaddition with simple hydroxylamines,l eading to the efficient formation of chiral b-lactam derivatives.

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Silyl peroxides as effective oxidants in the Baeyer–Villiger reaction with chloroaluminate(III) ionic liquids as catalysts

Cited by 17 publications

References 20 publications

W(OTf)₆‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid

W(OTf)₆‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid

Theoretical study on the structure and cation–anion interaction of triethylammonium chloroaluminate ionic liquid

Enantioselective Synthesis of Cyclopropanone Equivalents and Application to the Formation of Chiral β‐Lactams

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Silyl peroxides as effective oxidants in the Baeyer–Villiger reaction with chloroaluminate(III) ionic liquids as catalysts

Cited by 17 publications

References 20 publications

W(OTf)6‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid

W(OTf)6‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid

Theoretical study on the structure and cation–anion interaction of triethylammonium chloroaluminate ionic liquid

Enantioselective Synthesis of Cyclopropanone Equivalents and Application to the Formation of Chiral β‐Lactams

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W(OTf)₆‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid

W(OTf)₆‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid