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Imidazolium-based Ionic Liquid: An efficient, normalized and recyclable platform for Rh(III)-catalyzed directed C–H carbenoid coupling reactions Chen Zhang, Xiao-Mei Chen, Yi Luo, Jiang-Lian Li, Min Chen, Li Hai, and Yong Wu ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b03399 • Publication Date (Web): 27 Aug 2018 Downloaded from http://pubs.acs.org on August 27, 2018

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ACS Sustainable Chemistry & Engineering

Imidazolium-based Ionic Liquid: An efficient, normalized and recyclable platform for Rh(III)-catalyzed directed C–H carbenoid coupling reactions Chen Zhang, Xiao-Mei Chen, Yi Luo, Jiang-Lian Li, Min Chen, Li Hai* and Yong Wu*. Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy，Sichuan University, No.37. DaXue Road, Chengdu, Sichuan 610041, P.R. China. Correspondence: [email protected](Y. Wu); [email protected] (L. Hai) Keywords: Ionic Liquid • carbenoid coupling • Rh(III)-catalyzed • catalyst reusable • efficient and sustainable

Abstract: The ionic liquid [BMIM][NTf2] was developed as an ideal medium in which Rh(III)-catalyzed directed C–H carbenoid coupling reactions can conduct efficiently and sustainably. More significantly, the ionic liquid can not only achieve the recycle of catalyst system but also improve the efficiency of catalyst presenting that carbenoid coupling reactions can accomplish at room temperature with a short period of time. Thus, this work would be useful

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in expanding applications of C–H activation strategies as tools for assembling novel organic molecules.

Introduction Over the last 20 years, the C–H activation has become one of the most rapidly developing areas of homogeneous catalysis reshaping the landscape of synthetic chemistry

1-5

as it avoids

multi-step pre-activation of starting materials and minimizes the production of unwanted by-products.6-10 However, due to the high dissociation energy of C-H bonds (105 kcal/mol for methane and 110 kcal/mol for benzene), metal-mediation is often necessary.11-14 Most of metal catalysts (e.g., Pd, Rh, Ru and Ir) are expensive and earth-scarce. It drastically limited the extensive use of C–H activation strategies as tools for the synthesis of organic molecules. New protocols with outstanding cost efficiency, energy conservation and sustainable development in directed C-H activation have attracted increasing attention. One approach is to find inexpensive earth-abundant transition metals as alternative catalysts. For example, Co-catalyzed C-H activation15-18 pioneered by Nakamura, Ackermann, and Yoshikai have recently been applied in various transformations that were commonly catalyzed by Rh, Ru, and Pd. Although it can vastly reduce the cost, it still has limitations, for example, it cannot entirely replace noble metals for multifarious C–H activation. Another strategy is to find some ways to achieve recycling of transition metals and thereby authentically reduce the consumption of metals. Metal-immobilized macromolecular or nanometer materials19 have recently received attention, because metals can easily recycle and achieve cyclic utilization with lower costing and sustainable development. However, new metal complexes need multi-steps to synthesize and complex characterization.20-22 Thus, it is still highly desirable to develop a method with wide applicability and easy accessibility to solve these problems.


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Ionic liquids (ILs) have increasingly attracted interest in both academic and industrial fields.23-26 The special structure and interaction of ions endow them unique physicochemical properties, such as negligible vapor pressure, chemical, thermal and photocatalytic stability, nonflammability, low corrosivity and relatively high ionic conductivity. Given these properties, ionic liquids have been widely proposed as solvents for organic reactions at high temperature,27 thermal energy storage (TES)28, heat-transfer fluids (HTFs),29,30 high-temperature lubricants,31 propellants,32 and in analytical apparatus. In recent years, ILs have also been successfully used in chemical synthesis, such as for cross-coupling reactions

33-37

Therefore, ILs may be an ideal

medium of metal-mediated C-H activation reactions without organic solvents and pressure-tight equipment. Diazo compounds, due to their high and versatile reactivity, are important reagents in organic synthesis.38-43 One of their major applications is transition metal-catalyzed highly efficient carbon–carbon/carbon–heteroatom bond formation and allowing the construction of various carbocycles and heterocycles44-61 (Fig 1, a). We reported the diazo-methylene-diphosphonates couple with 2-phenylpyridines generating aromatic bisphosphonates, which were identified as potential β-lactamase inhibitors by combined computational and experimental assays62 (Fig 1, b). Continuing our interest in the carbenoid coupling reactions, we reported a protocol using IL as an efficient, stable and recyclable platform for Rh-catalyzed directed aryl C−H bond coupling of diazo compounds (Fig 1, c). The catalytic system and ionic liquid can be easily reused. More interestingly, the IL-based catalyst system enables substantial improvement of the reaction efficiency and carbenoid coupling reactions can conduct at room temperature with a short period of time.


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Figure 1, C-H coupling with diazo compounds.

Results and discussion Among the IL families, 1,3-disubstituted imidazolium salts exhibit unique properties due to their aromatic cation structures.63, 64 To begin, 2-phenylpyridine 1a (1 equiv) was treated with [Cp*RhCl2]2 (2.5 mol %), AgOAc (15 mol %), and diazomalonate 2a (1.2 equiv) in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]) (2 mL) at 60 °C for 12h, and the desired α-arylmalonate 3aa was obtained in 67% yield (Supplementary Table S1, entry 1). Encouraged by this result, other 1-butyl-3-methylimidazolium salts were tested. All of them were

suitable

for

the

reaction,

but

1-butyl-3-methylimidazolium

bis(trifluoromethanesulfonyl)imide ([BMIM][NTf2]) gave the highest yield (Table S1, entry 2-6). The reaction was equally effective at ambient temperature under air, although longer reaction time was required for complete reaction (Table S1, entry 7). Then, we found that the concentration of 1a vastly influenced the efficiency of coupling and 0.6 mol/L of 1a in [BMIM][NTf2] gave the best yield in 95% while the reaction time sharply declined to 2 hours at


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room temperature (Table S1, entry 8-12). Finally, other bis(trifluoromethanesulfonyl)imide ionic liquids with different cationic ions, including pyrrolidinium, piperidinium, pyridinium, guanidinium, and ammonium, were tested. (Table S1, entry 13-17). They all were effectual and triethylbutyl-ammonium bis((trifluoromethyl)sulfonyl)imide ([N2,2,2,4][NTf2]) also gave excellent yield (91%, Table S1, entry 17). Accordingly, after elementary optimization of the reaction conditions, the best conditions are as follows: 0.6 mol/L of 1a, 2.5 mol% [Cp*RhCl2]2, 15 mol% AgOAc in [BMIM][NTf2] at ambient temperature for 2 h. With the optimized conditions in hand, we investigated the substrates scope of 2-phenylpyridines and their analogues in the C-H coupling reactions with kinds of diazos (Scheme 1). First, 2-phenylpyridines with select substituents were tested with 2a. 2-Phenylpyridines with electron-donating substituents (e.g., Me, OMe and Ph) at different positions (ortho-, para-, or meta-position) of the 2-phenyl ring gave the desired products in excellent yields (86–96%, Scheme 1). Whereas electron-withdrawing groups containing 2-phenylpyridines (e.g., Cl, Br, F, NO2 and CF3) resulted in slightly lower yields (71-87%, Scheme 1). These results indicated that the coupling efficiency is to some extent influenced by the electron density of the aromatic ring. We then investigated the coupling efficiency of 2a with 2-(1-naphthalenyl)-pyridine (1l), 2-(2-naphthalenyl)-pyridine (1m) and 2-(thiophen-2-yl)pyridine (1n).They were all suitable for this transformation giving 3la–3na in 71%–95% yields. Finally, the scope of the diazoester coupling partners was also investigated. With 1a as the substrate, the Rh-catalyzed C−H coupling reactions with different 1,3-substituted diazo derivatives, including ethyl ester, acyl groups and diethyl phosphonate (2c−2h), furnished the desired products 3ac− 3ah in 58−97% yields (Scheme 1). Scheme 1. Rh(III)-catalyzed directed C–H coupling of 2-Aryl-pyridines with diazos.a


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a

Reaction conditions: 1 (0.2 mmol), 2 (0.24 mmol), [Cp*RhCl2]2 (2.5 mol%), AgOAc (15 mol%), [BMIM][NTf2] (0.3 mL), room temperature, 2 hours under an air atmosphere; b Reaction time extended to 12 h; c Reaction time extended to 24 h; d Using Ag2SO4 (10 mmol%) as Ag salt. Then, directing groups (e.g., heterocycles, oximes, azo and carbonylrelated functional groups) have been employed for this catalytic arene C-H functionalization (Scheme 2). First, substrates with directing N-containing six-membered rings were tested, including 2-phenylpyrimidine (4a), 1-(pyrimidin-2-yl)-1H-indole (4b), 3-methoxy-6-phenyl-pyridazine (4c) and benzo[h]quinolone (4d). These substrates showed high reactivity in this transformation (62%-80%, 5aa-5da, Scheme 2). Then, five-membered N-containing heterocyclic compounds were also used to expand

substrate scope of the protocol.

Treatment

of 1-phenyl-1H-pyrazole (4e),

2-phenyl-2H-1,2,3-triazole (4f) and 5,5-dimethyl-2-phenyl-2,5-dihydrooxazole (4g) with 2a under the optimized conditions afforded respective products 5ea-5ga in 67−91% yield. In addition, benzaldehyde O-methyl oxime (4h) and azobenzene (4i) were viable substrates for this


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reaction furnishing the desired products 5ha-5ia in moderate to high yields. Finally, the insertion product 5ja was attained when benzoic acid (4j) was test as a substrate, indicating that the carbene insertion reactions into X–H were still working in ionic liquid under this condition. Scheme 2. Scop of directing groups a

a

Reaction conditions: 4 (0.2 mmol), 2 (0.24 mmol), [Cp*RhCl2]2 (2.5 mol%), AgOAc (15 mol%), [BMIM][NTf2] (0.3 mL), room temperature, 2 hours under an air atmosphere; b Using AgSbF6 (10 mmol%) as Ag salt; c Reaction time extended to 12 h and reaction temperature up to 50 °C; d Reaction time extended to 24 h. Due to the pervasive applications of diazo compounds in assembling many heterocycles, we also studied the efficacy of carbenoid coupling formation annulation in ionic liquid. As is shown in table 1, those cyclization reactions preformed spectacularly and gave multifarious heterocycles in good to excellent yield. The N-replaced benzamides were treated with ethyl diazoacetoacetate 2b under standard conditions and obtained isoquinolinones smoothly. When 2b was switched to


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diazotized Meldrum’s acid (2i), N-methoxyisoquinolinediones 7bi was given. Isoquinolin-3-ols 7cb can be acquired when ethyl benzimidate 6c and 2b were treated together and AgSbF6 was used to replace AgOAc. Except for isoquinoline derivatives, it was facile synthesis of cinnolines as 1-methyl-1-phenylhydrazine was reacted with 2b. Together, these results lead us to conclude that the strategy of Rh(III)-catalyzed directed carbenoid coupling reactions in the ionic liquid is suitable for a wide range of substrates. In contrast to all previous reports about carbenoid coupling reactions and cyclization reactions45-62, only we need is the catalytic system of [Cp*RhCl2]2 and Ag salts, rather than omnifarious solvents and addictives. So the ionic liquid is a highly efficient and succinct platform which kinds of carbenoid coupling reactions can triumphantly conduct and realize routinization. Table 1. Scope of useful DGs: straightforward access towards heterocyclic nitrogen a


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a

Reaction conditions: 6 (0.2 mmol), 2b (0.24 mmol), [Cp*RhCl2]2 (2.5 mol%), AgOAc (15 mol%), [BMIM][NTf2] (0.3 mL), room temperature, 2 hours under an air atmosphere; b Using AgSbF6 (10 mmol%) as Ag salt; c Reaction time extended to 24 h; d Using diazotized meldrum’s acid (2i) instead of 2b. To investigate the potential of this procedure in practical synthetic contexts, the gram scale experiment and reuse of catalytic system study were then examined. As expected, 3aa was isolated in 88% yield when treating 1a (1.0 g) with 2a in 4ml ionic liquid using 1 mol% catalyst (Scheme 3). To test stabilities and recyclability of this protocol, the feasibility of recycling the catalyst system and ionic liquid was studied with 6d and 2b as substrates. After completion of the reaction, the product was simply separated by extraction and the remains were further subjected to vacuum to remove the rest of solvents before it was reused in subsequent reactions. The following reactions can conduct smoothly and need to add nothing but new substrates. Then we focused on the impact of extraction solvents on recycling. As described in Figure 2, n-heptane and cyclohexane are the best solvents. After they were reused five times, there was no notable loss of its catalytic activity (Figure 2). Scheme 3. The gram scale experiment

Figure 2, The study about impact of extraction solvents on recycling.


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Yield

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90% 80% 70%

cyclohexane

60%

n-heptane

50%

1-chlorobutane

40% toluene

30%

ether

20% 10% 0% 1

2

3

4

5

Runs

Experiments were then performed to investigate the reaction mechanism. In the presence of [BMIM][NTf2]/CD3OD (9:1), H/D exchange at the ortho-position of 1a was not observed, suggesting irreversible C-H activation (Scheme 4, a), which probably meant the C-H activation step was different with Yu’s work44. Next, competition experiments with 1c and 1e were used to investigate the electronic preference of the reaction. The reaction displayed a 3ca:3ea yield ratio to 4:1, implying that the electron-rich arenes reacted faster (Scheme 4, b). This is consistent with a slightly asynchronous C−H insertion and an electrophilic aromatic substitution mechanism, with Ar−Rh interaction, rather than the acidity of an ortho-C−H bond as the predominant factor dictating the efficiency of the C-H activation step. Finally, a significant kinetic isotope effect (KIE) was observed from an intermolecular competition assay (KH/KD = 19.0), supporting the C− H activation probably as rate-limiting step (Scheme 4, c). Scheme 4. primary mechanism studies.


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Based on the mechanistic studies and the relevant reports44, a plausible mechanistic pathway was depicted in Figure 3. Firstly, anion exchange between [Cp*RhCl2]2 and Ag salt generates an active catalyst I, which undergoes C−H bond cleavage to form a rhodacyclic intermediate II. Coordination of the diazo compound with II may form the diazonium intermediate III. Extrusion of N2 would afford intermediate IV. Next, the migratory insertion of carbene into the rhodium– carbon bond affords V. Finally, protonolysis of V generates the desired product and the active Rh. Figure 3, The proposed mechanism.


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DG R1

1/2 [Cp*RhCl2]2 R2

AgOAc

DG

Cp*Rh(OAc)2

Cp* Rh DG

R1

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I

R2

V

Rate-limiting step Migratory insterion

Cp* DG AcO Rh II

Cp* DG Rh

R1 IV

R1

R2 N2

N2 metal carbene formation

N

R1 N

R2

Cp* DG Rh R2 III

Conclusion In summary, a mild and efficient protocol for direct Rh(III)-catalyzed C–H carbenoid coupling reactions in [BMIM][NTf2] was developed. Compared with previous reports, this protocol provides a catalyst recyclable, and normalized approach toward carbenoid coupling reactions with advantages of good functional group tolerance, broad substrate scope, shorter reaction time, and without additional heating. Moreover, this method may open up an alternative that ionic liquids would be an ideal platform of the C–H activation. We anticipate that this discovery would conduce to the more extensive use of C–H activation strategies as tools for constructing novel chemical molecules in academia and industry. Experimental section Supporting Information: full experimental details (general information about experiments, preparation of substrates and experimental procedures), characterization data and spectra of products


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General procedure for the synthesis of 3aa To a 5 ml tube was added 1a (30 mg, 0.19 mmol), 2a (42 mg, 0.23 mg), [Cp*RhCl2]2 (2.9 mg, 2.5 mol%), AgOAc (4.8 mg, 15 mol%) in [BMIM][NTf2] (0.3 mL). The tube was sealed and stirred at room tempereture for 2 h. After completion, the reaction mixture was extracted with Et2O. After extraction and evaporation of the solvents under reduced pressure, the crude product was purified by column chromatography on silica gel (PE/EtOAc: 10:1) to get white solid 3aa (95% yield). Corresponding Author *E-mail: [email protected] *E-mail: [email protected]. ORCID Yong Wu: 028-85503235 Present Addresses No.37. DaXue Road, Chengdu, Sichuan 610041, P.R. China. Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Funding Sources This work was supported by National Natural Science Foundation of China (Grant No: 81773577; 81573286)


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Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We thank Prof. Yong Wu for helpful discussions and preliminary experiments. ABBREVIATIONS [BMIM], 1-butyl-3-methylimidazolium;

[BF4],

bis(trifluoromethyl)-sulfonyl

[N2,2,2,4][NTf2]

amide;

fluoroboric

acid;

[NTf2],

triethylbutyl-ammonium

bis((trifluoromethyl)sulfonyl)imide REFERENCES 1. 2. 3.

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For Table of Contents Use Only.

C-H carbenoid coupling reactions can perform in ionic liquid at room temperture and metal catalyst can be easily reused


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Imidazolium-Based Ionic Liquid - ACS Publications - American

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