Natural Product Glycine Betaine as an Efficient Catalyst for

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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 ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b01287 • Publication Date (Web): 20 Jun 2017 Downloaded from http://pubs.acs.org on June 26, 2017

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ACS Sustainable Chemistry & Engineering

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 E-mails: [email protected], [email protected]

ABSTRACT: Transformation of carbon dioxide (CO2) into value-added chemicals is of great importance, and use of natural product as the catalyst is very interesting. Herein, we used the naturally occurring glycine betaine as an efficient and renewable catalyst for the formation of 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

ACS Paragon Plus Environment


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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 in 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 and 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 oC) and/or high pressures (>5 MPa) are generally needed in the reaction. Mild conversion of CO2 with amines to form N-substituted 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 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, non-toxic, and renewable catalytic systems for the synthesis of N-substituted compounds is highly desirable. Additionally, CO2 (C+4) could be reduced with organosilanes and hydroborane through successive two-electron reduction steps to generate the corresponding C+2, C0 and C−2 products.50-54 Thus,


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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 biodegrade, harmless and cheap raw material, glycine betaine has been employed as catalyst,57,58 medicine,59,60 and 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 catalyst for the synthesis of N-substituted compounds using CO2 as the carbon resource with organosilanes as the reductant.31,51 However, to the best of our knowledge, biodegrade glycine betaine has not yet been used as the catalyst in this kind of important reaction.

Scheme 1. The chemical structure of glycine betaine.

Herein, we reported that glycine betaine could be used as an efficient, biodegrade, 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.

RESULTS AND DISCUSSIONS



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Initially, to prove the catalytic activity of glycine betaine, formylation of N-methylaniline with CO2 and PhSiH3 to N-methylformanilide 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 electron-donating groups on the para-position (entries 3 and 4, Table 1) showed much higher reactivity than those with electron-withdrawing groups (entries 5-7, Table 1). Meanwhile, para-substituted 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 down 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 corresponding 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.


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Table 1. Formylation of various secondary amines using CO2 as the carbon source.a Entry Substrate Product Time (h) C (%)b Y (%)b 1c

NH

N

2

NH

N

CHO

CHO

3 4

N CHO

O

O

NH

CHO

Cl

5 6

N

N CHO

Br

Br

N

N CHO

O2N

7

N CHO CHO N

8

S (%)b

4

99

95 (93)d

95

6

>99

95

95

4

>99

98 (94)d

98

12

>99

91

91

10

92

83

90

12

32

23

72

4

>99

82

82

12

21

3

15

12

92

77

84

4

71

54

76

6

95

81

85

4

>99

>99 (95)d

>99

4

96

91

95

6

>99

95

95

O

N

CHO

10

H N

11

H N

CHO

H N

CHO

12 13

a

CHO

H N

9

N

N

4

O

N

4

4

NH

14

H N

15

N

O

4

N CHO

NH

N N

CHO

Reaction conditions: substrate, 0.5 mmol; PhSiH3, 1 mmol; CO2, 0.5 MPa; CH3CN, 1 mL; room

temperature; amountof glycine betaine, 3 mol%. bC=Conversion, Y=Yield, S=Selectivity. C and Y were determined by GC using biphenyl as the internal standard. cNo glycine betaine was added. dThe values in parentheses were the isolated yields.



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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 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 mono-formylated formamides. However, 2,6-diisopropylaniline (Entry 5, Table 2) showed relative lower conversion and mono-formylated product yield because of the steric hindrance effect of the substituent groups. Table 2. Formylation of various primary amines using CO2 as the carbon source.a

Entry

Substrate

1 2

NH2

O

NH2

C (%)b

Y (%)b a

b

98

85

10

>99

86

10

O

3

NH2

98

92

3

4

NH2

98

91

3

5

NH2

80

43

19

87

81

3

98

91

5

87

81

4

NH2

6 7 8 a

O

NH2

NH2

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.


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In the search for novel catalytic processes of CO2 conversion in organic synthesis, the complete deoxygenation of CO2 is of great interest to access non-carbonyl 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 oC, 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 labelling 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 betaine (Table 4) by changing the reaction conditions (100 oC, 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). Table 3. Methylation of various N-methylamines using CO2 as the carbon source.a H N R

Entry 1

Substrate NH

CHO + CO2

R

Product N

N

+

R

N

C (%)b

Y (%)b

S (%)b

94

80 (77)c

85



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2

NH

N

>99

62

62

3

O

NH

O

N

>99

44

44

4

Cl

NH

Cl

N

81

64

79

>99

62 (59)c

62

>99

46

46

>99

60

60

>99

78

78

0

0

--

N H

5

N

H N

6

N

NH

7

N

H N

8

4

9d a

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N

4

4

4

NH

N

Reaction conditions: reactant, 0.5 mmol; PhSiH3, 2 mmol; CO2, 0.3 MPa; CH3CN, 1 mL; temperature,

100 oC; 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. c

The values in parentheses were the isolated yields. dThe reaction was conducted without using CO2.

Table 4. Formation of aminals from N-methylanilines using CO2 as the carbon source.a H N R

Entry 1 2

Substrate NH

+ CO2

Product N N

NH

N

N

N R

R

b

C (%)

Y (%)b

S (%)b

93

84(80)c

90

84

61(56)c

73

N

a

Reaction conditions: reactant, 1 mmol; PhSiH3, 2 mmol; CO2, 0.2 MPa; CH3CN, 1 mL; temperature, 100

o

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. cThe values in parentheses were the isolated yields.

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


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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 oC, 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 oC 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 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 was 1:2:2 at 100 oC, the bis(silyl)acetal was formed, which could react with amine rapidly to form aminal as the main product. When the amine : PhSiH3 : CO2 was 1:4:6 at 100 oC, the bis(silyl)acetal could be further reduced by PhSiH3 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. Firstly, 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 N-methylaniline 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 N-methylaniline



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and glycine betaine by forming an intermediate (I in Scheme 2), which could activate the N-H bond in N-methylaniline, and thus was helpful for the subsequent reaction. Secondly, it was found that there was no difference for 1H signal of 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 N-methylaniline was added into the mixture of PhSiH3 and glycine betaine, the 1H signal of Si-H proton shifted from 4.18 ppm to 4.19 ppm, suggesting that there existed interaction between these three compounds. We believed that the 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 the Si-H and the cation group in glycine betaine to form an intermediate II (Scheme 2), and thus favored the insertion of CO2 into the 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. The intermediate II could activate the Si-H bond in PhSiH3. Then, the 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 silyl active species to form a new C-N bond to generate the corresponding products.


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R1

O

-

H

H

O R2

N+

H

Intermediate I

CO2

Intermediate II Ph

O

Si H

O

PhSiH3

Ph

O

O

Si H2

O Ph and/or H H

Bis(silyl)acetal

Intermediate I R2

R2

N

N

R1

R2

R1 Aminals

Formamides

R2

PhSiH3

Si

Ph

O

CH3 O

CH3

H3C Methoxysilane

Intermediate I

O N

O N+

N

O

Silyl formates

R1

H

Intermediate II

Si H2

H

-

H Si

Ph

H

R1

O

N

Intermediate I

R1

N

R2

Methylamines

Scheme 2. The possible reaction mechanism for the synthesis of N-substituted compounds using CO2 as the C1 building block over glycine betaine.

CONCLUSIONS In conclusion, glycine betaine can be used as the efficient catalyst for the formation of 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 biodegrade basic catalyst has great potential of application for 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 Supporting Information Experimental Section, Activity of various hydrosilanes, 13C NMR spectra for an isotopic labelling experiment, GC-MS spectra for the active species, 1H NMR spectra for mechanism discussion. These materials are available free of charge via the Internet at http://pubs.acs.org.



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AUTHOR INFORMATION Corresponding Author *E-mails: [email protected], [email protected] Notes The authors declare no competing financial interest.

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

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Synopsis: Naturally occurring glycine betaine could efficiently catalyze the transformation of CO2 to produce various N-substituted compounds with amines and PhSiH3.


Natural Product Glycine Betaine as an Efficient Catalyst for

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