A Facile Procedure for Acetalization of Aldehydes and Ketones Catalyzed by Cerium(III) Trifluoromethanesulfonate

Ono, Fumiaki; Inatomi, Yoshiko; Tada, Yuusuke; Mori, M.; Sato, Tsuneo

doi:10.1246/cl.2009.96

Cited by 9 publications

(4 citation statements)

References 19 publications

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“…2 Because of the versatility and usefulness of acetals in organic synthesis, several methods for the protection [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] and the selective, mild deprotection 21 of aldehydes and ketones have been described. The classical procedure for protection involves the Lewis [3][4][5][6][7][8][9][10][11][12][13][14][15] or protic acid-catalyzed [16][17][18][19][20] reaction of a carbonyl compound with a large excess of an alcohol in the presence of a water scavenger. Among the employed Lewis acids are metal triflates, [3][4][5][6][7][8] 19 and silica-supported HClO 4 20 have been used as protic acids.…”

Section: Introductionmentioning

confidence: 99%

“…The classical procedure for protection involves the Lewis [3][4][5][6][7][8][9][10][11][12][13][14][15] or protic acid-catalyzed [16][17][18][19][20] reaction of a carbonyl compound with a large excess of an alcohol in the presence of a water scavenger. Among the employed Lewis acids are metal triflates, [3][4][5][6][7][8] 19 and silica-supported HClO 4 20 have been used as protic acids. Despite the advocated advantages of several recently described methods for the acetalization reaction, they have some drawbacks, such as the use of toxic, strong and corrosive acids, non-recyclable catalysts, volatile organic solvents (VOCs) and, in some cases, non-commercially available catalysts.…”

Section: Introductionmentioning

confidence: 99%

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The use of anhydrous CeCl3 as a recyclable and selective catalyst for the acetalization of aldehydes and ketones

Silveira¹,

Mendes²,

Ziembowicz³

et al. 2010

J. Braz. Chem. Soc.

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Um método eficiente, limpo, quimiosseletivo e sem a utilização de solventes para a síntese de dimetil acetais de aldeídos e cetonas foi desenvolvido usando ortoformiato de trimetila e CeCl 3 anidro como catalisador. O método é geral e, sob condições reacionais brandas, fornece compostos carbonílicos protegidos em bons rendimentos, incluindo aril e alquil cetonas e aldeídos. O catalisador pode ser reutilizado diretamente, três vezes, sem perda significativa da atividade.An efficient, clean, chemoselective and solvent-free method for the synthesis of ketone and aldehyde dimethyl acetals was developed using trimethyl orthoformate and commercially available anhydrous CeCl 3 as a recyclable catalyst. The method is general and affords the protected carbonyl compounds in good yields and under mild conditions, including aryl and alkyl ketones and activated aldehydes. The catalyst could be utilised directly for 3 cycles, without significant loss of activity.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The use of anhydrous CeCl3 as a recyclable and selective catalyst for the acetalization of aldehydes and ketones

Silveira¹,

Mendes²,

Ziembowicz³

et al. 2010

J. Braz. Chem. Soc.

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“…Additionally, these molecules are water-compatible catalysts, an important property for reactions such as acetalization/ketalization, which generate water as a byproduct (Scheme ). Indeed, Sc(OTf) 3 , Ce(OTf) 3 , and Yb(OTf) 3 are known to catalyze acetalizations/ketalizations under mild conditions. We recently found that Lu(OTf) 3 is an efficient catalyst for acetone ketalization with glycerol .…”

Section: Introductionmentioning

confidence: 99%

Origins of the Regioselectivity in the Lutetium Triflate Catalyzed Ketalization of Acetone with Glycerol: A DFT Study

et al. 2015

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We describe DFT computations that address the regioselective preference toward the five-membered ring product 1,3-dioxolane (solketal) over the six-membered-ring product (1,3-dioxane) during Lu(OTf) 3 -catalyzed ketalization of acetone with glycerol. When ketalization occurs via the internal (secondary) −OH group of glycerol, only solketal production should be possible due to the symmetry of the intermediates. Ketalization via the terminal −OH group of glycerol is predicted to occur in a different manner than the conventionally proposed ketalization mechanism. A constrained hemiketal intermediate is invoked to explain the selectivity for solketal formation.

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“…In recent years, green catalysis has been found to be the method of choice for the production of acetals. For instance, researchers have used many catalysts for the acetalization of carbonyl compounds such as, lanthanum(III)nitrate hexahydrate (Srinivasulu et al, 2008), bismuth subnitrate (Wu et al, 2008), anhydrous CeCl 3 (Silveira et al, 2010), cerium(III) trifluoromethanesulfonate (Ono et al, 2009) tetrafluoroboric acid adsorbed on silica gel (Kumar et al, 2008) and phosphotungstic acid and its cesium salt supported on dealuminated ultra-stable Y zeolites (Zhang et al, 2006).…”

Section: Introductionmentioning

confidence: 99%

Catalytic acetalization of carbonyl compounds over cation (Ce3+, Fe3+ and Al3+) exchanged montmorillonites and Ce3+-exchanged Y zeolites

Thomas

Ramu

Gopinath

et al. 2011

Applied Clay Science

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Under ambient reaction conditions, a one-pot acetalization of carbonyl compounds with methanol was carried out over a series of solid acid catalysts. Ion-exchanged montmorillonite samples were prepared by a metal cation (Ce 3+ , Fe 3+ and Al 3+) exchange from the activated K-10 montmorillonite. These materials have been characterized by wide-angle X-ray scattering (WAXS), solid-state nuclear magnetic resonance spectroscopy (solid-state NMR), temperature programmed desorption of ammonia (NH 3-TPD) and Brunauer-Emmett-Teller (BET) analysis. The catalytic results of montmorillonites were compared with those of H-Y, Ce,Na-Y, Ce,H-Y zeolites, SiO 2 and γ-Al 2 O 3. Irrespective of the catalyst, the reaction yields the corresponding dimethoxyacetal in high yield. Comparison of the catalytic activity indicates that the montmorillonite catalysts are the most active catalysts for the reaction. The molecular size of the carbonyl substrates is one of the significant factors in determining the acetalization ability of the catalysts, and the activity of ketones follow the order cyclohexanone N 4-nitroacetophenone N acetophenone N 4-methoxybenzophenone N benzophenone. In the aromatic carbonyl compounds, the electron donor or acceptor properties of the substituents are also critical to the reactivity of the acetophenones and benzaldehydes. The aldehydes considered in the present investigation exhibit an activity order of 4-nitrobenzaldehydeN benzaldehyde N 4-methoxybenzaldehyde, which substantiates that electron-withdrawing groups favor the reaction. The reaction time studies indicate that the montmorillonite catalysts are more resistant to deactivation, predominantly due to the superior pore diffusional properties of these materials compared to microporous zeolites.

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A Facile Procedure for Acetalization of Aldehydes and Ketones Catalyzed by Cerium(III) Trifluoromethanesulfonate

Cited by 9 publications

References 19 publications

The use of anhydrous CeCl3 as a recyclable and selective catalyst for the acetalization of aldehydes and ketones

The use of anhydrous CeCl3 as a recyclable and selective catalyst for the acetalization of aldehydes and ketones

Origins of the Regioselectivity in the Lutetium Triflate Catalyzed Ketalization of Acetone with Glycerol: A DFT Study

Catalytic acetalization of carbonyl compounds over cation (Ce3+, Fe3+ and Al3+) exchanged montmorillonites and Ce3+-exchanged Y zeolites

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