Natural Product Glycine Betaine as an Efficient Catalyst for

Research Article pubs.acs.org/journal/ascecg

Natural Product Glycine Betaine as an Efficient Catalyst for Transformation of CO2 with Amines to Synthesize N‑Substituted Compounds Chao Xie,†,‡ Jinliang Song,*,† Haoran Wu,†,‡ Baowen Zhou,† Congyi Wu,† and Buxing Han*,†,‡ †

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, No. 2 Zhongguancun, North First Street, Haidian District, Beijing 100190, P. R. China ‡ School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, 19A Yuquan Road, Shijingshan District, Beijing 100049, P. R. China S Supporting Information *

ABSTRACT: Transformation of carbon dioxide (CO2) into value-added chemicals is of great importance, and use of natural products as a catalyst is very interesting. Herein, we used the naturally occurring glycine betaine as an efficient and renewable catalyst for the formation of a C−N bond between CO2 and amines using PhSiH3 as the reductant. The effects of different factors on the reaction were studied. It was demonstrated that the catalyst was very active for the reactions, and a broad range of amine substrates could be converted with satisfactory yields. Moreover, the selectivity to different N-substituted compounds could be controlled by the molar ratio of reactants (i.e., CO2, amines, and PhSiH3) and the reaction temperature. In the catalytic cycle, the carbon oxidation state of CO2 could be reduced to +2, 0, and −2, respectively, and thus, the corresponding formamides, aminals, and methylamines were produced via successive two-electron reduction steps. KEYWORDS: Transformation of carbon dioxide, C−N bond formation, Amines, Glycine betaine, Reduction

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INTRODUCTION Carbon dioxide (CO2) is an abundant and renewable C1 building block for the synthesis of value-added chemicals.1−7 Much effort has been devoted to the field of CO2 transformation, and a series of valuable chemicals, e.g., carbonates,8−14 alcohols,15−18 urea derivatives,19−22 carboxylic acids,23,24 polymers,25−28 and N-substituted compounds,29,30 have been synthesized using CO2 as the carbon resource. One of the promising routes for CO2 conversion is the synthesis of N-substituted compounds (e.g., formamides, aminals, and methylamines) through the C−N bond formation between CO2 and amines in the presence of various reductants because these N-substituted compounds are widely used in medicines, agrochemicals, dyes, etc.31−37 With H2 as the reductant, formamides and methylamines can be obtained from the reaction of CO2 and amines catalyzed by metal-based catalysts.38,39 However, high temperatures (>100 °C) and/or high pressures (>5 MPa) are generally needed in the reaction. Mild conversion of CO2 with amines to form Nsubstituted compounds is highly attractive in both academia and industry.40−42 In recent years, organosilanes have been employed as a class of efficient reductants for converting CO2 to form N-substituted compounds under milder reaction conditions.43,44 In this aspect, the synthesis of formamides and methylamines from CO2 conversion has attracted much © 2017 American Chemical Society

interest, and diverse catalysts have been developed, including N-heterocyclic carbenes,45 metal complexes,46 ionic liquids,47 organic molecule catalysts,48,49 and solvent catalytic systems.30,40,50 In contrast, less attention has been paid to the formation of aminals by the reaction of CO2 with amines, and only an organic base51 and iron complex52 have been applied in this route. Although the above catalytic systems have been reported, development of efficient, nontoxic, and renewable catalytic systems for the synthesis of N-substituted compounds is highly desirable. Additionally, CO2 (C4+) could be reduced with organosilanes and hydroborane through successive twoelectron reduction steps to generate the corresponding C2+, C0, and C2− products.50−54 Thus, how to balance the reactivity and the product selectivity is another key point for the synthesis of the three N-substituted compounds from the reaction of CO2 and amines. Nowadays, increasing attention has been paid to the utilization of naturally occurring or biomass-derived compounds as sustainable catalysts or solvents.55,56 Glycine betaine, widely existing in plants, is a kind of quaternary ammonium alkaloid possessing a zwitterionic structure (Scheme 1). As a Received: April 25, 2017 Revised: May 30, 2017 Published: June 20, 2017 7086

DOI: 10.1021/acssuschemeng.7b01287 ACS Sustainable Chem. Eng. 2017, 5, 7086−7092

ACS Sustainable Chemistry & Engineering

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Scheme 1. Chemical Structure of Glycine Betaine

Research Article

RESULTS AND DISCUSSION

Initially, to prove the catalytic activity of glycine betaine, formylation of N-methylaniline with CO2 and PhSiH3 to Nmethylformanilide was used as a model reaction at 0.5 MPa CO2 and room temperature. No reaction occurred without any catalyst (entry 1, Table 1), while the reaction could be completed at the same reaction conditions when 3 mol % glycine betaine was added (entry 2, Table 1), suggesting the catalytic effect of glycine betaine. Delighted by this desired result, formylation of various N-methylanilines with CO2 via a 2-electron reduction to the corresponding N-methylformanilides was further examined, and most N-methylanilines were successfully formylated with good to excellent yields with different reaction times. Nonetheless, substrates with electrondonating groups on the para-position (entries 3 and 4, Table 1) showed much higher reactivity than those with electronwithdrawing groups (entries 5−7, Table 1). Meanwhile, parasubstituted N-methylanilines (entry 4, Table 1) showed a higher selectivity than the ortho-substituted ones due to the steric hindrance effect of the substituent group. In addition, it was found that the presence of two phenyl groups on the nitrogen atom slowed the formylation of the N−H bond in diphenylamine (entry 9, Table 1), while two benzyl on the nitrogen atom still provided a good yield (entry 10, Table 1). Furthermore, glycine betaine could also catalyze the formylation of aliphatic secondary amines, including dipropylamine, dihexylamine, and morpholine to form the correspond-

biodegradable, harmless, and cheap raw material, glycine betaine has been employed as a catalyst,57,58 in medicine,59,60 and as a food additive.61,62 Due to its basicity, glycine betaine has great potential to be used as a basic catalyst. Generally, basic catalysts are the most used catalysts for the synthesis of Nsubstituted compounds using CO2 as the carbon resource with organosilanes as the reductant.31,51 However, to the best of our knowledge, biodegradable glycine betaine has not yet been used as a catalyst in this kind of important reaction. Herein, we reported that glycine betaine could be used as an efficient, biodegradable, and readily available basic catalyst for the construction of C−N bonds from CO2 and amines using phenylsilane (PhSiH3) as the reductant. By controlling the reaction conditions, the oxidation state of carbon in CO2 can be effectively converted to +2, 0, and −2 to form formamides, aminals, and methylamines, respectively.

Table 1. Formylation of Various Secondary Amines Using CO2 as the Carbon Sourcea

a

Reaction conditions: substrate, 0.5 mmol; PhSiH3, 1 mmol; CO2, 0.5 MPa; CH3CN, 1 mL; room temperature; amount of glycine betaine, 3 mol %. C = Conversion, Y = Yield, S = Selectivity. C and Y were determined by GC using biphenyl as the internal standard. cNo glycine betaine was added. d Values in parentheses were isolated yields. b

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is noteworthy that there was a competition between mono- and bis-formylated products for primary amines because both N−H bonds could be reactive. Glycine betaine could also catalyze the formylation of most of aromatic primary amines (entries 1−4, Table 2) and aliphatic amines (entries 6−8, Table 2) with good to excellent conversions of amines and yields of monoformylated formamides. However, 2,6-diisopropylaniline (entry 5, Table 2) showed relatively lower conversion and mono-formylated product yield because of the steric hindrance effect of the substituent groups. In the search for novel catalytic processes of CO2 conversion in organic synthesis, the complete deoxygenation of CO2 is of great interest to access noncarbonyl compounds. 63 As mentioned above, CO2 can be converted with amines to form aminals and methylamines (two complete deoxygenation products) via 4-electron reduction and 6-electron reduction, respectively. Since glycine betaine showed efficient activity for formylation of amines with CO2, we attempted to use glycine betaine as the catalyst for the synthesis of aminals and methylamines using CO2 as the carbon resource and PhSiH3 as the reductant. To our delight, glycine betaine could indeed catalyze methylation of N-methylamines with CO2 to form N,N-dimethylamines (Table 3). Through a 6-electron reduction pathway, various N,N-dimethylamines could be generated from the corresponding N-methylanilines and aliphatic secondary amines by adjusting the reaction conditions (100 °C, 0.3 MPa CO2, 3 mol % glycine betaine, and 4 equiv. PhSiH3). In order to confirm the methyl source was CO2 rather than glycine betaine, we conducted the isotopic-labeling experiment for the methylation of N-methylaniline using 13CO2 as the carbon source. The results from 13C NMR spectra (Figure S1) and GC-MS (Figure S2) indicated that CO2 was the methyl source. Meanwhile, a control experiment without using CO2 (entry 9, Table 3) showed that no N,N-dimethylaniline was generated, further confirming the methyl source was CO2. More interestingly, aminals, 4-electron reduction products, could also be formed from CO2 and N-methylanilines over glycine

ing formamides with good yields (entries 11−13, Table 1). More importantly, the unsaturation amine trans-1-cinnamylpiperazine (entry 15, Table 1) could also be formylated without destroying the double bond in this glycine betaine catalytic system. In addition, other hydrosilanes showed no activity for the formylation of N-methylaniline (Table S1), suggesting the priority of PhSiH3 for this reaction. Since glycine betaine was found to be highly effective for the formylation of various secondary amines with CO2, we further expanded the substrate to different primary amines (Table 2). It Table 2. Formylation of Various Primary Amines Using CO2 as the Carbon sourcea

a Reaction conditions: reactant, 0.5 mmol; PhSiH3, 1 mmol; CO2, 0.5 MPa; CH3CN, 1 mL; room temperature; reaction time, 6 h; amount of glycine betaine, 3 mol %. bC = Conversion, Y = Yield. C and Y were determined by GC using biphenyl as the internal standard.

Table 3. Methylation of Various N-Methylamines Using CO2 as the Carbon sourcea

Reaction conditions: reactant, 0.5 mmol; PhSiH3, 2 mmol; CO2, 0.3 MPa; CH3CN, 1 mL; temperature, 100 °C; reaction time, 6 h; amount of glycine betaine, 3 mol %. bC = Conversion, Y = Yield, S = Selectivity for the methylation products. C and Y were determined by GC using biphenyl as the internal standard. cValues in parentheses were the isolated yields. dReaction was conducted without using CO2.

a

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ACS Sustainable Chemistry & Engineering Table 4. Formation of Aminals from N-Methylanilines Using CO2 as the Carbon sourcea

Reaction conditions: reactant, 1 mmol; PhSiH3, 2 mmol; CO2, 0.2 MPa; CH3CN, 1 mL; temperature, 100 °C; reaction time, 4 h; amount of glycine betaine, 1.5 mol %. bC = Conversion, Y = Yield, S = Selectivity. C and Y were determined by GC using biphenyl as the internal standard. cValues in parentheses were the isolated yields.

a

Scheme 2. Possible Reaction Mechanism for Synthesis of N-Substituted Compounds Using CO2 as the C1 Building Block over Glycine Betaine

betaine (Table 4) by changing the reaction conditions (100 °C, 0.2 MPa CO2, 1.5 mol % glycine betaine, and 2 equiv. PhSiH3), and the obtained aminals could be identified by GC-MS (Figure S3 and S4). The above results indicated that the formation of formamides, aminals, and methylamines could be controlled by the reactant ratios and the reaction temperature. In our reaction system, 0.2 MPa CO2 in a 22 mL stainless reactor was about 2 mmol. When the molar ratio of amine, PhSiH3, and CO2 was 1:2:10 under room temperature, the formamide was the principal product with a small amount of methylamine formed (entry 1, Table 1), and no aminal was detected. When the molar ratio of amine, PhSiH3, and CO2 was changed to 1:2:2 and the temperature was increased to 100 °C, the principal product was aminal with N,N-dimethylamine and formamide as the side products (entry1, Table 4). Furthermore, the principal product became N,N-dimethylamine with only formamide as the side product (entry1, Table 3) at 100 °C when the molar ratio of amine, PhSiH3, and CO2 was 1:4:6. Generally, the reactant molar ratio and the reaction temperature affected the type of the silyl active species, and thus, the main product could be tuned by the molar ratio and temperature. Typically, when PhSiH3 is reacted with excessive CO2, a CO2 molecule could only react with a phenylsilane, and the main intermediate is silyl formates. If the reductant is excessive, the silyl formates could be further reduced into bis(silyl)acetal, formaldehyde, and methoxysilane. Therefore, when the amine:PhSiH3:CO2 ratio was 1:2:10 at room temperature, the active species was the silyl formates (Figure

S5), and thus, formamide was the main product. However, when the amine:PhSiH3:CO2 ratio was 1:2:2 at 100 °C, the bis(silyl)acetal was formed, which could react with amine rapidly to form aminal as the main product. When the amine:PhSiH3:CO2 ratio was 1:4:6 at 100 °C, the bis(silyl)acetal could be further reduced by PhSiH 3 to form methoxysilane (Figure S6), and thus, methylamine was the main product. To achieve more detailed insight into the role of glycine betaine on the reaction, NMR analysis was performed on the interaction of glycine betaine with N-methylaniline, PhSiH3, and CO2. First, the 1H NMR spectra of N-methylaniline and its mixture with glycine betaine (Figure S7) showed that the 1H signal intensity of the N−H proton (4.34 ppm) in Nmethylaniline decreased significantly in the presence of glycine betaine, and the 1H signal of N−CH3 (2.77 and 2.76 ppm) changed from a double peak to a single peak (2.77 ppm). These results indicated that there was strong interaction between Nmethylaniline and glycine betaine by forming an intermediate (I in Scheme 2), which could activate the N−H bond in Nmethylaniline, and thus was helpful for the subsequent reaction. Second, it was found that there was no difference in the 1H signal of the Si−H proton (4.18 ppm) between PhSiH3 and the mixture of PhSiH3 and glycine betaine (Figure S8), indicating that there was no strong interaction. However, when Nmethylaniline was added into the mixture of PhSiH3 and glycine betaine, the 1H signal of the Si−H proton shifted from 4.18 to 4.19 ppm, suggesting that there was an interaction between these three compounds. We believed that the 7089



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ACKNOWLEDGMENTS The authors thank the National Natural Science Foundation of China (21673249, 21533011), Chinese Academy of Sciences (QYZDY-SSW-SLH013), and Youth Innovation Promotion Association of CAS (2017043).

interaction between N-methylaniline and glycine betaine weakened the intramolecular interaction between anion and cation groups in glycine betaine, which was beneficial for the interaction of Si−H and the cation group in glycine betaine to form an intermediate II (Scheme 2) and thus favored the insertion of CO2 into Si−H to form the active species for subsequent reactions. Finally, we found no new signal or chemical shift in the 1H and 13C NMR spectra of the mixture of glycine betaine and CO2, indicating that glycine betaine could not activate CO2 noticeably. On the basis of the above results and the related knowledge in the literatures,50,53,54,64 a possible mechanism for the glycine betaine catalyzed hydrosilylation of CO2 with amine to produce formamides, aminals, and methylamines was proposed (Scheme 2). In the catalytic cycle, glycine betaine could interact with amines and PhSiH3 to form the intermediates I and II. Intermediate II could activate the Si−H bond in PhSiH3. Then, CO2 was inserted into the activated Si−H bond to form different silyl active species, depending on the molar ratio of the reactants and the reaction temperature. Meanwhile, the N−H bond in amines could also be activated by glycine betaine by the formation of intermediate I. Finally, the activated nucleophilic N atom in amines attacks the carbon atom of the silyl active species to form a new C−N bond to generate the corresponding products.

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CONCLUSIONS In conclusion, glycine betaine can be used as an efficient catalyst for the formation of a C−N bond between CO2 and amines using PhSiH3 as the reductant. By controlling the molar ratio of reactants (i.e., CO2, amines, and PhSiH3) and the reaction temperature, the carbon oxidation state of CO2 can be controlled to be +2, 0, and −2, respectively, and the corresponding formamides, aminals, and methylamines are generated from successive two-electron reduction steps. We believe that the renewable, greener, and biodegradable basic catalyst has great potential for application in the transformation of CO2 to the N-substituted products, and glycine betaine can be used as the catalyst for some other base-catalyzed reactions. ASSOCIATED CONTENT

S Supporting Information *

These materials are available free of charge via the Internet at The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.7b01287. Experimental section, activity of various hydrosilanes, 13C NMR spectra for an isotopic labeling experiment, GCMS spectra for the active species, and 1H NMR spectra for mechanism discussion. (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (J. Song). *E-mail: [email protected] (B. Han). ORCID

Jinliang Song: 0000-0001-9573-600X Buxing Han: 0000-0003-0440-809X Notes

The authors declare no competing financial interest. 7090


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