PEG–SO3H as an efficient and reusable catalyst for chemoselective synthesis of 1,1-diacetates

doi:10.1016/j.cclet.2013.01.007

Chinese Chemical Letters

Volume 24, Issue 2, February 2013, Pages 140-142

https://doi.org/10.1016/j.cclet.2013.01.007 Get rights and content

Abstract

An efficient and convenient procedure of the synthesis of 1,1-diacetates from aromatic aldehydes and acetic anhydride under mild and solvent-free conditions at room temperature, in the presence of PEG–SO₃H is reported. PEG–SO₃H acts as a catalyst and can be recovered and reused eight times without apparent loss of its catalytic activity.

Graphical abstract

The synthesis of 1,1-diacetates from aromatic aldehydes and acetic anhydride in the present of PEG–SO₃H as efficient catalyst is described. The catalyst can be recovered and reused eight times.

Introduction

The synthesis of 1,1-diacetates is one of the most versatile acylal-formation reactions in modern organic synthesis. Since 1,1-diacetates are stable toward a wide range of nucleophiles under neutral and basic conditions, acetylation is commonly utilized as a protecting method for carbonyl groups [1]. Moreover, they also serve as valuable precursors for the asymmetric allylic alkylation reactions [2] in natural product synthesis [3], and for the synthesis of 1-acetoxydienes and 2,2-dichlorovinylacetates for Diels–Alder reactions [4], [5]. Acylals have also been used as cross-linking agents for cellulose in cotton [6]. Therefore, the methods for their synthesis have received considerable attention. Generally, 1,1-diacetates are synthesized from aldehydes and acetic anhydride using a variety of protic acids such as methanesulfonic [7], sulfuric [5], or perchloric acid [8]. However, in many cases, the yields are poor.

Recent years have witnessed the intensive investigation of this reaction using various Lewis acids such as Fe(NO₃)₃·9H₂O [9], cupric sulfate [10], In(OTf)₃ [11], P₂O₅/Al₂O₃ [12], LiOTf [13], Bi(NO₃)₃ [14], Al(HSO₄)₃ [15]. Several reusable heterogeneous catalysts for the reaction have also been reported such as titanium modified MCM-41 [16], Keggin heteropolyacid [17], sulfuric acid [3-(3-silicapropyl)sulfanyl]propyl ester [18], silica-bonded N-propylsulfamic acid [19], polymer-supported gadolinium triflate [20], silica-bonded S-sulfonic acid [21], ZSM-5-SO₃H [22], different solid acids [23], solid silica sulfuric acid [24], and Brønsted acidic ionic liquids under ultrasonic irradiation [25].

Although some of these methods afford good to high yields of the corresponding diacetates, the majority suffers from one or more of the following limitations: prolonged reaction time or low yields, high temperature, use of harmful organic solvents, or use of moisture-sensitive and costly catalysts. Previously, our group has reported the Biginelli-type reaction using PEG–SO₃H as a catalyst and solvent under microwave irradiation [26]. The PEG–SO₃H catalyst is water-stable, non-corrosive, environmentally benign and recyclable [27], [28].

In order to continue our work, based on our previous research [26], [29], [30], herein, we wish to describe PEG–SO₃H as a catalyst for the synthesis of aromatic 1,1-diacetates.

Section snippets

Experimental

All reagents were obtained from commercial vendors and used without further purification. Melting points were determined on an XT-4 electrothermal micromelting point apparatus and the thermometer was uncorrected. PEG–SO₃H was prepared according to the previously reported procedure [26]. IR spectra were recorded using KBr pellets on Nicolet AVATAR 36 FT-IR spectrophotometer. NMR spectra were recorded at 400 (¹H) and 100 (¹³C) MHz, respectively, on a Varian Mercury plus-400 instrument using CDCl₃

Results and discussion

The PEG-bound sulfonic acid catalyst was prepared by reacting PEG-6000 with excess chlorosulfonic acid according to the literature procedures [27]. The conversion of the terminal hydroxyl groups on the PEG was determined to be quantitative by ¹H NMR analysis (Fig. S1, see supporting information), and the singlets at δ 12.85 and 4.23 were assigned to the proton of SO₃H and the α-methylene protons at the polymer attached site, respectively. The IR spectra of PEG–SO₃H and PEG6000 are illustrated

Conclusion

The reactions to synthesize 1,1-diacetates from aldehydes and acetic anhydride were efficiently catalyzed by PEG–SO₃H under solvent-free conditions. The catalyst can be recovered and reused at least eight times without apparent loss of activity. It should be noted that PEG–SO₃H has high catalytic activity, and that only 5 mol% of PEG–SO₃H is sufficient to catalyze the reaction in most cases. These results not only provide a new aspect of catalytic organic reactions, but also extend the utility

Acknowledgments

This work was financially supported by Key Laboratory of Hexi Corridor Resources Utilization of Gansu Universities (No. XZ1011), the President's Funds of Hexi University (No. XZ-2009-9) and the National Natural Science Foundation of China (No. 21262010).

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Original articlePEG–SO3H as an efficient and reusable catalyst for chemoselective synthesis of 1,1-diacetates

Abstract

Graphical abstract

Introduction

Section snippets

Experimental

Results and discussion

Conclusion

Acknowledgments

J. Mol. Catal. A Chem.

Tetrahedron Lett.

Tetrahedron

Appl. Catal. A Gen.

Tetrahedron Lett.

Chin. J. Chem.

Tetrahedron Lett.

Monatsh. Chem.

Tetrahedron

Synth. Commun.

Catal. Lett.

Chin. Chem. Lett.

Protecting groups in organic synthesis. Part 8. Conversion of aldehydes into geminal diacetates

J. Org. Chem.

gem-Diacetates as carbonyl surrogates for asymmetric synthesis. Total syntheses of sphingofungins E and F

J. Am. Chem. Soc.

The Chemistry of acylals. 3. Cyanohydrin esters from acylals with cyanide reagents

Org. Lett.

Original article
PEG–SO₃H as an efficient and reusable catalyst for chemoselective synthesis of 1,1-diacetates