3-Bromo-1,1,1-trifluoro-2-propanol assisted chemical fixation of CO2 and epoxides

Journal Pre-proofs 3-Bromo-1,1,1-trifluoro-2-propanol assisted chemical fixation of CO2 and epoxides Hui Ma, Ji-jun Zeng, Dong-huai Tu, Wei Mao, Bo Zhao, Kuan Wang, Zhao-tie Liu, Jian Lu PII: DOI: Reference:

S0040-4039(20)30002-2 https://doi.org/10.1016/j.tetlet.2020.151593 TETL 151593

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Tetrahedron Letters

Received Date: Revised Date: Accepted Date:

14 November 2019 29 December 2019 3 January 2020

Please cite this article as: Ma, H., Zeng, J-j., Tu, D-h., Mao, W., Zhao, B., Wang, K., Liu, Z-t., Lu, J., 3-Bromo-1,1,1trifluoro-2-propanol assisted chemical fixation of CO2 and epoxides, Tetrahedron Letters (2020), doi: https:// doi.org/10.1016/j.tetlet.2020.151593

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3-Bromo-1,1,1-trifluoro-2-propanol assisted chemical fixation of CO2 and epoxides

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Hui Maa,b, Ji-jun Zenga, Dong-huai Tua, Wei Maoa, Bo Zhaoa, Kuan Wangb, Zhao-tie Liub,c,, Jian Lua,b, O O CO2

R1

R2

3-BTFP/TBAI 45 oC, 0.5 MPa, 24 h

O R1

O R2

1

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3-Bromo-1,1,1-trifluoro-2-propanol assisted chemical fixation of CO2 and epoxides Hui Maa,b, Ji-jun Zenga, Dong-huai Tua, Wei Maoa, Bo Zhaoa, Kuan Wangb, Zhao-tie Liub,c,, Jian Lua,b, State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi'an Modern Chemistry Research Institute, Xi'an 710065, China; College of Chemistry and Chemical Engineering, Shaanxi University of Science & Technology, Xi'an 710021, China c School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China a b

———

A R T I C L E I Nauthor. F O E-mail: [email protected](Jian B S TLu), R [email protected] CT  Corresponding (Zhao-tie Liu). Article history: Received Received in revised form Accepted Available online

Keywords: 3-bromo-1,1,1-trifluoro-2-propanol chemical fixation cyclic carbonates hydrogen bonding interaction

3-bromo-1,1,1-trifluoro-2-propanol (3-BTFP) in combination with n-butylammonium iodide (TBAI) was proved to be an efficient organocatalyst for chemical fixation of CO2 with various epoxides to the respective cyclic carbonates. A possible reaction mechanism was proposed wherein 3-BTFP activated epoxide through hydrogen bonding interaction. This mechanism is revealed by the results of FT-IR spectra and 1H NMR titration, and the synergetic effect functioned by 3-BTFP and TBAI ensures the reaction proceeding effectively. Herein, 3-BTFP represents a commercially available, stable and metal-free hydrogen-bonding donor for CO2 transformation, which has a potential application for the large-scale synthesis of cyclic carbonates.

1. Introduction Carbon dioxide is the main greenhouse gas contributor, which is also a ubiquitous, nontoxic and renewable C1 feedstock.1 With the increasing environmental, economic and social concerns, research on converting CO2 into valuable chemicals has received enormous attention over the past decades.2 The chemical fixation of CO2 to cyclic carbonates can be considered as one of the most promising strategies because of theoretical 100% atom efficiency and eco-friendly.3 Also, these cyclic carbonates have been extensively used as electrolytic elements in lithium secondary batteries, precursors for polymer synthesis, polar aprotic solvents, and intermediates for the manufacture of pharmaceuticals and fine chemicals.4 So far, various catalysts have been developed for this chemical fixation to produce cyclic carbonates,5 where tetraalkylammonium halides are one of the most intensively investigated organocatalysts.3b,6 However, harsh reaction conditions are usually required to achieve high CO2 conversion, along with limited substrates in the presence of above-mentioned catalysts. Recently, it has been proved that introducing hydrogen bond donors (HBDs) to tetraalkylammonium salts is an efficient approach to improve the reaction performance and HBDs containing hydroxyl exhibit superior properties to other HBDs.712 In this aspect, Zhang and coworkers developed a dual catalyst system based on 1,2-benzenediol and n-Bu4NI (TBAI). As a result, the chemical fixation of CO2 with epoxides could proceed smoothly under 3 MPa CO2 and 115 ℃ .8 Wilhelm reported on the use of pentaerythritol as a kind of HBDs, allowing the synthesis of cyclic carbonates at 4 bar and 70 °C. 9 Subsequently,

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a breakthrough in reducing the reaction temperature (45 ℃-50 ℃) was achieved when (multi)phenolic compound pyrogallol or cavitand-based polyphenols as HBDs were employed.10 Unfortunately, these systems required methyl ethyl ketone, a solvent with high flammability. Compared with phenolic compounds, work by Tassaing has shown that fluoroalcohols, especially 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene or perfluoro-tert-butanol, exhibited excellent catalytic activity. But 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene was difficult to obtain, and perfluoro-tert-butanol had high odor level and evaporation rate with high toxicity, thus limiting their large-scale application.11 Very recently, several other HBDs containing hydroxyl such as dinaphthyl-silanediol, 2hydroxymethylpyridine, hydroxypyridines and boronic acids have been reported.12 Despite their potential effectiveness, some disadvantages are present including well-designed but tedious preparation, poor stability and expensive price.13 Therefore, the development of new organocatalysts, which are easily available, highly effective and stable, still represents a challenging task. 3-Bromo-1,1,1-trifluoro-2-propanol (3-BTFP) is a cheap, nontoxic and commercially available fine chemical, which has been applied as fire extinguishing agent and synthetic intermediate for materials and medicines.14 As an important halogenated alcohol, 3-BTFP with trifluoromethyl group and Br atom could be potentially used as an excellent hydrogen-bonding donor. However, to the best of our knowledge, effort on its application in CO2 fixation has not yet been reported. Herein, we report an efficient process for chemical fixation of CO2 　 catalyzed by a new organocatalytic system 3-BTFP/TBAI under mild conditions. It is demonstrated that 3-BTFP could activate the

2

2. Results and Discussion

indicating that the cooperative effect between the hydroxyl group and iodide anion efficiently promoted the cycloaddition reaction. In addition, it was noted that the selectivity to AGC always sustained above 98%. Hence, 3-BTFP coordinated with TBAI was further investigated in followed tests.

2.1. Screening of Catalysts

2.2 Effects of Reaction Parameters

CO2

O

TBAX (5 mol%), HBDs (5 mol%) 35 oC, 0.5 MPa, 24 h

O O

O

X= I, Br, Cl

Entry 1 2 3 4 5 6 7 8 9 10 11 12 13

Catalytic system 3-BTFP 3-BTFP/TBAC 3-BTFP/TBAB 3-BTFP/TBAI TBAI H2O/TBAI CH3CHOHCH3 /TBAI CH3CH2CH2OH /TBAI CH2FCH2CH2OH/TBAI CH2BrCH2CH2OH/TBAI CF3CH2CH2OH/TBAI CF3CHBrCH2OH/TBAI CF3CH(OMe)CH2Br/TBAI

Yield (%)b trace 47 61 76 44 44 46 49 52 57 55 64 45

Selectivity (%)b 99 99 98 98 98 98 98 98 98 98 98 98

Reaction conditions: AGE (14.3 mmol), tetrabutylammonium salts (5 mol%), HBDs (5 mol%), CO2 0.5 MPa, 35 ℃, 24 h. bDetermined by GC using 1,3,5-trimethyoxybenzene as internal standard. a

Initially, the chemical fixation of CO2 and allyl glycidyl ether (AGE) into 4-allyloxymethyl-1,3-dioxolan-2-one (AGC) was chosen as a model reaction. The corresponding results are summarized in Table 1. Almost no activity in forming the cyclic carbonate AGC was observed when the reaction was carried out using 3-BTFP alone (Table 1, entry 1). Surprisingly, the catalytic behaviors of 3-BTFP combined with different quaternary ammonium salts vary considerably. As seen in Table 1, the yields of AGC approachs 47%, 61% and 76% respectively (entries 2-4). This catalytic activity is enhanced with the increase of halide anion leaving ability at the order of I-> Br-> Cl-, which is in accordance with previous reports.6b,h,12b,c,15 The 3-BTFP/TBAI catalytic system was the best for the reaction, while the sole TBAI gave a 44% yield (Table 1, entry 5). Next, water and a series of alcohols in combination with TBAI were screened. The AGC yield was not improved when 5 mol% H2O was used as HBD (Table 1, entry 6). When n-PrOH and i-PrOH were employed, AGC could be afforded in 46% and 49% respectively (Table 1, entries 7 and 8). Compared with n-PrOH, we found that higher yields were observed with 3-fluoropropanol, 3bromopropanol and 3.3.3-trifluoro-1-propanol (Table 1, entries 9-11). As reported elsewhere, the hydrogen bonding capability of the alcohol increases with the number of electron-withdrawing fluorine atom increasing, thus affecting the activating efficiency of fluorinated alcohols.16 These results clearly show that halogenated alcohols are more reactive in contrast to unsubstituted alcohols. Noticeably, the binary system 2-bromo3,3,3-trifluoro-1-propanol/n-butylammonium iodide remarkably improved the catalytic activity, and the yield of AGE reached to 64%. Interestingly, 3-BTFP has been found to give better catalytic activity than 2-bromo-3,3,3-trifluoro-1-propanol, this sequence is quite different from that of the results using 2propanol and 3-propanol (Table 1, entries 4, 7, 8, 12). Furthermore, 2-methoxy-3-bromo-1,1,1-trifluoropropane bearing hydroxyl-protecting group with TBAI only gave a 45% yield, significantly lower than 3-BTFP/TBAI (Table 1, entry 13 vs. 4),

Selectivity (%)

Yield (%) 100

95 80

90

Yield and Selectivity (%)

O

(B)

100

85 80 75 70 65 60

Yield (%) Selectivity (%)

55

60

40

20

0

50 25

(C)

30

35

40

45

1-1

50

Temperature (℃)

(D)

100

2-2

3-3

4-4

5-5

Catalyst loading (mol %) 100 90 80

90

Yield and selectivity (%)

O

(A)

Yield and selectivity (%)

Table 1. Catalyst screening for the chemical fixation of CO2 and AGE a.

Yield and selectivity (%)

epoxides through hydrogen bonding interaction, combining with the nucleophilic synergetic effect of iodide ion, which greatly promote the cycloaddition.

80

70

60

Yield (%) Selectivity (%)

70 60 50 40 30 20

Yield (%) Selectivity (%)

10 0

50 0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

5

10

CO2 pressure (MPa)

15

20

25

Reaction time (h)

Figure 1 Effects of reaction parameters on the chemical fixation of CO2 and AGE: (A) temperature, (B) catalyst loading, (C) CO2 pressure and (D) reaction time. Unless otherwise mentioned, reaction conditions: AGE (14.3 mmol), 3-BTFP (5 mol%), TBAI (5 mol%), CO2 0.5 MPa, 45 ℃, 24 h.

The effects of reaction parameters on the chemical fixation were investigated. As shown in Fig. 1A, the AGC yield is strongly affected by the reaction temperature and it is dramatically improved from 60% to 97% by raising the temperature from 25 °C to 45 °C. While further increasing the temperature led to a slight change in the yield. Based on these results, 45 °C was adopted for further investigation. To evaluate the effect of catalyst loading, a series of experiments were carried out by varying the amount of 3-BTFP and TBAI (1:1) and the results were depicted in Fig. 1B. AGC was provided in 56% yield when as low as 1 mol% of catalyst (relative to the AGE) was used. It is clear that the catalyt system 3-BTFP/TBAI is effective for the synthesis of AGC. Above 4 mol%, the increase trend of yield became lower. With a further increase of catalyst loading to 5 mol%, a comparable 97% of AGC was obtained. Hence, 5 mol% should be a good choice. As illustrated in Fig. 1C, the AGC yield is sensitive to CO2 pressure in the low pressure from 0.1 to 0.5 MPa, but it remains nearly constant at medium CO2 pressures of 1.0 to 4.0 MPa. A similar effect of CO2 pressure on catalytic activity has been observed before.17 The initial increase of CO2 pressure leads to an increase of CO2 concentration in the liquid phase and thus improves the AGC yield. However, with the increasing of CO2 pressure, a certain amount of AGE is extracted into the vapor phase and causes the reduction of AGE concentration in the liquid phase, which gives rise to the constant AGC yield. In this regard, 0.5 MPa was suitable for AGC synthesis. The dependence of reaction time was examined at 45 °C and 0.5 MPa CO2 pressure (Fig. 1D). The reaction time also has a significant influence on the reaction yield. With the reaction time prolonged from 3 h to 21 h, the AGC yield achieved from 14% to 93%. Afterwards, there appeared only a slight rise in AGC yield, thus 24 h was the optimal time for the reaction in this work. 2.3. Catalytic Activity towards Other Epoxides

3 loss of stereochemistry was observed when diastereomerically pure cis- or trans-1k was employed as starting material. However, the stereochemistry of 2l was exclusively the cis-isomer, which has been determined by the 13C NMR, 1H NMR and NOESY NMR.6g,18

Table 2 Chemical fixation of CO2 with various epoxides catalyzed by 3-BTFP/TBAI a O O CO2

R1

Entry

R2

O

1a

H3C

O

1e

98

90

98

97

98

93

99

2f

ClH2C

O

O

O

ClH2C

1g

As illustrated in Table 1, the combination of 3-BTFP and TBAI is essential for the chemical fixation of CO2 with epoxide and the synergetic roles played by 3-BTFP and TBAI ensure that the reaction proceeds effectively. In order to gain a deeper insight into the reaction mechanism over the binary 3-BTFP/TBAI system, FT-IR spectra and 1H NMR were employed to verify the role of 3-BTFP. As shown in Fig. 2, the addition of AGE to 3-BTFP causes downfield shifting of the stretching vibration of hydroxyl group, and it gradually moves from 3425.2cm-1 to 3383.9cm-1. However, AGE has no characteristic absorption peak at these sites, suggesting that 3-BTFP activates the epoxide through the proposed hydrogen-bonding interactions. Further evidence for the formation of the intermolecular hydrogen bond is obtained from the results of 1H NMR of different molar ratios of AGE and 3-BTFP. The chemical signals of hydroxyl hydrogen of 3-BTFP clearly shift from 2.8 to 3.0, then to 3.3, finally to 3.5, indicating that hydrogen bonds between 3-BTFP and AGE are formed. The 1H NMR results are consistent with the FT-IR analysis. a

2g O

b

O

O

1h

O

c

89

99

3383.9

2h O O

O

F3C

97

99

O

O

3500

95

cis-1k

2000

1500

1000

500

a

2.5

3.0

3.5

4.0

4.5

b

O

O

2500

98

O

H3C

3000

Wavenumber (cm )

2i CH3

3417.3

-1

O

10d

O

e

3425.2

2j

1i

d

3386.5

O

O

O

87

98

CH3

2.5

3.0

3.5

4.0

4.5

c

2k (cis/trans=31:69) e O

O O

CH3

trans-1k

O

H3C

56

98

2.5

3.0

3.5

4.0

4.5

d

CH3

2k (cis/trans=10:90) e O

O

H

13d

86 O O

O

BrH2C

1f

H 3C

99

O

O

1j

12d

91

2e

BrH2C

H 3C

O

O

O

11d

99

2d O

F3C

94

O

O

O

9c

98

2c

1d

O

97

O

O

1c

8

Selectivity (%)

2b O

4

7

O

O

O

6

Yield (%)

O

O

1b

5c

2.4. Proposed Reaction Mechanism b

2a

H3C

3

R2

O

O

O

2

O

b

Products

O

O

O R1

Epoxides

1

3-BTFP/TBAI 45 oC, 0.5 MPa, 24 h

O

O

H

71

98

1l

2l aReaction conditions: epoxides (14.3 mmol), 3-BTFP (5 mol%), TBAI (5 mol%), CO2 0.5 MPa, 45 ℃, 24 h. bDetermined by GC using 1,3,5-trimethyoxybenzene as internal standard. c90 ℃. d70 ℃. eQuantified by NMR of the crude reaction mixture.

To evaluate the efficiency and generality of the organocatalyst, the experiments of other substituted epoxides with CO2 were examined as illustrated in Table 2. The binary 3-BTFP/TBAI catalysts display outstanding efficiency and various epoxides bearing electron-donating and electron-withdrawing groups can furnish the desired products 2a-j in good to excellent yields and high selectivities (Table 2, entries 1-9). With the increase of steric hindrance from side chains, the catalytic activities decline, however, satisfactory yields are also obtained at the expense of high reaction temperature (Table 2, entries 10-12). Notably, a

2.5

3.0

3.5

4.0

2.5

3.0

3.5

4.0

e

4.5

4.5

Figure 2 The IR and 1H NMR spectra of different molar ratios of [AGE]/[3BTFP]:(a) pure AGE; (b)[AGE]/[3-BTFP]=5:1; (c)[AGE]/[3-BTFP]=1:1; (d) [AGE]/[3-BTFP]=1:5; (e) pure 3-BTFP

It is well known that the activation of the epoxide by a hydrogen bond donor accelerates the conversion with carbon dioxide. Based on the previous mechanistic investigation on chemical fixation7-10 and above experimental results, a plausible mechanism is proposed as shown in Scheme 1. Firstly, the hydroxyl function group of 3-BTFP interacts with the oxygen atom of AGE through hydrogen bonding interaction, which leads to polarization of the C-O bond, and the activated epoxide simultaneously is attacked by the iodide anion as nucleophile from the less sterically hindered-carbon atom, thus facilitating the ring opening of the epoxide. As a result, the hydrogen bondingstabilized alkoxide I is produced. Subsequently, CO2 inserted into

4 the intermediate I and leads to a new alkyl carbonate anion II. Finally, the cyclic carbonate is formed via an intramolecular ringclosure and the catalyst is regenerated. O CF3

3.

R

HO

CF3

Br O O

R

R

4.

Bu4N I CF3

O O

O

Br

O

R

H

O

Bu4N I

O I

H

CF3

O

NBu4

（II）

O

Br

Br CO2

H

NBu4

O

I

R

（I）

5.

Scheme 1 Proposed mechanism for the chemical fixation reaction of CO2 and epoxides.

3. Conclusion The efficient organocatalyst composed of 3-BTFP and TBAI has been developed for the chemical fixation between epoxides and CO2 to afford the five-membered cyclic carbonates under solvent-free conditions. Under optimized reaction conditions of 5 mol% 3-BTFP and 5 mol% TBAI, 0.5 MPa of CO2 , after 24 h at 45 °C and an excellent yield of AGC of 97% can be achieved. As confirmed by FT-IR and 1H-NMR analysis, there is an interaction between 3-BTFP and epoxide. A possible mechanism for the chemical fixation referring to the synergistic action of hydroxyl group and iodide ion is suggested. The binary 3BTFP/TBAI system is applied to various epoxides, even the low active epoxides such as 1,1,1-Trifluoro-2,3-epoxypropane and cyclohexene oxide. The catalytic system is easily available and exhibits excellent stability, which displays the potential application for the large-scale synthesis of cyclic carbonates.

Acknowledgments The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (21978160, 21776170), Shaanxi Key Research and Development Program (2016MSZD-G-3-3). Supplementary data

6.

7.

8. 9.

Supplementary data associated with this article can be found in the online version, at http://dx.doi.org/xxx. References and notes 1.

2.

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10. 11.

12.

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Highlights: • 3-bromo-1,1,1-trifluoro-2-propanol was

3-Bromo-1,1,1-trifluoro-2-propanol assisted chemical fixation of CO2 and epoxides

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Hui Maa,b, Ji-jun Zenga, Dong-huai Tua, Wei Maoa, Bo Zhaoa, Kuan Wangb, Zhao-tie Liub,c,, Jian Lua,b, O O CO2

R1

R2

3-BTFP/TBAI 45 oC, 0.5 MPa, 24 h

proved to be an excellent hydrogen-bonding donor for CO2 transformation. • Synergistic effects of hydroxyl group and iodide anion render the reaction performing at 0.5MPa CO2. • The reaction could be carried out under solvent- and metal-free conditions. • A broad scope of cyclic carbonates could be obtained in high yield.

O R1

O R2