Cycloaddition reaction of spiro-epoxy oxindole with CO2 at

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Letter

Cycloaddition reaction of spiro-epoxy oxindole with CO2 at atmospheric pressure using deep eutectic solvent RAJ KUMAR TAK, Parth Patel, Saravanan Subramanian, Rukhsana I. Kureshy, and Noor-ul H. Khan ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b02566 • Publication Date (Web): 06 Aug 2018 Downloaded from http://pubs.acs.org on August 7, 2018

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ACS Sustainable Chemistry & Engineering

Cycloaddition reaction of spiro-epoxy oxindole with CO2 at atmospheric pressure using deep eutectic solvent Raj Kumar Tak,†, ‡ Parth Patel,†, ‡ Saravanan Subramanian,§ Rukhsana I. Kureshy,*,†, ‡ Noor-ul H. Khan,†, ‡ †

Inorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals Research

Institute, G. B. Marg, Bhavnagar – 364002, Gujarat, India. ‡

Academy of Scientific and Innovative Research, CSIR-Central Salt and Marine Chemicals

Research Institute, Council of Scientific & Industrial Research (CSIR), G. B. Marg, Bhavnagar – 364002, Gujarat, India. §

Department of Chemistry, School of Chemical and Biotechnology, SASTRA Deemed

University, Thirumalaisamudram, Thanjavur-613401, Tamilnadu, India. *

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

Abstract Developing a strategy to synthesize an unprecedented and previously unknown organic molecule is especially appealing. The design, synthesis and development of a new class of spiro-cyclic carbonates are reported. An efficient process involving the cycloaddition reaction of spiroepoxyoxindoles with CO2 [balloon] has been demonstrated using deep eutectic solvent [DES]. The reaction can be carried out under mild reaction conditions to afford desired spiro-cyclic carbonates in excellent yields [up to 98%]. The product could be separated easily and the DES was reusable for four times with retention of its activity. Keywords Carbon dioxide, Deep eutectic solvent, Spiro-epoxy oxindole, Spiro-cyclic carbonates.

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Introduction Nature has evolved with rich diversity of organic molecules and creation of similar molecular architectures are long standing fascination of chemists. In this consequence, developing a methodology for the facile synthesis of novel and unique small organic molecule is an intellectually challenging exercise. It is difficult to overstate the importance of the privileged spiro-skeletons, since it represents a significant class of biologically and pharmaceutically active bicyclic compounds.1-5 In spite of their wide spread bioactivities, functionalities such as spiro-epoxy oxindoles are also potential to serve as versatile synthon for generating new molecular entities. In chemical conversion of spiro-epoxy oxindoles, recently catalytic system were developed for the ring-opening reaction of epoxides using various nucleophiles to form a 3,3-di-substituted-oxindoles [Figure 1]. In 2011, Nair et al. reported the aminolysis of spiro-epoxyoxindoles at 30 oC for the synthesis of 3-hydroxy-3aminomethylindolin-2-ones.6 Later, Hajra et al. reported the ring opening of spiroepoxyoxindoles with indoles in presence of Sc(OTf)3 and used this protocol for the synthesis of (+/-)-gliocladin C a fungal derived marine alkaloid. 7 Furthermore, Wei and Hajra’s extended this work with phenol as a nucleophile in presence of FeCl 3/Sc(OTf)3 for the synthesis of the inhibitor of sodium channel Nav1.7 (+/-)-XEN402.8,9 Recently, Wang et al. reported the ring opening of spiro-epoxyoxindoles with ammonia for the synthesis of dioxibrassinin and spirobrassinin analogues.10 In contrast to this paradigm, the ring expansion of epoxide in spiro-epoxy oxindole is unusual and not explored so far. On the other hand, cycloaddition of carbon dioxide to epoxide is a promising strategy to effectively utilize the renewable energy in the chemical production chain.11-15 Conversion of carbon dioxide in the preparation of cyclic carbonate is an atom-economical, environmentally benign reaction and


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a topic of great interest.16,17 To date, a number of catalytic systems including metal18-23 and organobased homogeneous24-30 and heterogeneous catalytic systems,

ammonium salts,31-34 ionic

liquids35-37 and deep eutectic solvents [DES]38-50 have been reported for internal and external epoxides. Among the different catalytic systems, ionic liquids received considerable attention for the production of cyclic carbonate due to their unusual properties. However, there is a constant pursuit of developing green alternatives for the traditional ionic liquids. Remarkably, the DESs possess analogues properties of the ILs such as green, biodegradable and can be prepared easily in any scale by mixing hydrogen bond donor [HBD] and hydrogen bond acceptor [HBA] in proper molar ratio.38 DES is well-known for its green nature, CO2 philicity and its activity on cyclic carbonate formation, still there are much rooms for improvement in terms of substrate compatibility and practicability. In particular, cyclic carbonates with different skeletons such as spiro based could be interesting scaffolds and we envisioned that such a molecular construct will enable new directions by tailoring the design and properties. Thus, herein we document the first efficient functionalization of spiro-epoxy oxindole motif via cycloaddition pathway to achieve the spiro-cyclic carbonate using choline chloride and urea, a deep eutectic green solvent [Figure 1]. Result and discussion At the outset of our work, we synthesized spiro-epoxy oxindole substrates using trimethylsulfoxonium iodide and cesium carbonate at 50 ◦C in acetonitrile6 [Figure 1]. In this process of starting material synthesis, we tried to replace acetonitrile with environmentally benign solvents such as 2-methyl tetrahydrofuran and ethanol, but neither of these solvent produced good yield as acetonitrile. So, the same procedure as reported was followed for the synthesis of spiroepoxy oxindole substrates.



Figure 1. Spiro-epoxy oxindole as a synthon for 3,3-disubstituted 2-oxindole derivatives and our approach for the synthesis of spiro-cyclic carbonate. Various substituted substrates were synthesized in quantitative yields and used for the synthesis of cyclic carbonate. These substrates have been previously synthesized and studied for its ring opening reaction of epoxide in oxindole derivatives, using various nucleophile6-10 but not been investigated for the ring-expansion. Our investigation begin with the preparation of deep eutectic solvents [DESs]38 with different combination of HBDs such as urea, glycerol, ethylene glycol and benzoic acid with choline chloride [ChCl] as HBAs in molar ratio of [1:2] [Scheme 1].

Scheme 1. Synthesis of deep eutectic solvents based on choline chloride [1 equiv.] and hydrogen donor molecule in [1:2].


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DES is considered as an emergent class of solvents formed by the intermolecular interactions. Given our previous experience in cyclic carbonate formation reaction, 51-53 we screened the activity of synthesized DESs using N-benzyl spiro-epoxy oxindole 1a as a model substrate to optimize the reaction conditions [Table 1]. The substrate spiro-epoxy oxindole was first examined for the ring expansion using CO 2 [1 atm] at mild reaction conditions [40 oC] in presence of series of DESs. It should be noted here that in the absence of DES there is no conversion [Table 1, entry 1]. Interestingly, DES with the combination of choline chloride and urea served better for the conversion compared to other HBDs such as glycerol, ethylene glycol and benzoic acid [Table 1, entries 2-5]. This is due to the better solubility of CO2 in ChCl [1]: urea [2] [0.301 molCO2/ molDES] mixture.39,40,54-56 Having confirmed the activity for the formation of cyclic carbonate, we turned our attention to increase the yield by investigating other reaction parameters. Considering the inherent problems of forming bicyclic rings, we attempted to study the effect of temperature which might be suitable for reducing the activation barrier. Notably, by increasing the temperature from 40 to 70 oC [Table 1, entries 6-8] the yield of spiro-cyclic carbonate increased significantly [98%] in 5h [entry 8]. We then investigated the amount of ChCl:urea [100 to 300 mg] required for the spiro-cyclic carbonate formation and observed that 300 mg resulted in the maximum yield [98%] in shorter reaction time [Table 1, entry 10]. Table 1. Optimization condition for cycloaddition reaction of n-benzyl spiro-epoxy oxindole with CO2.[a]



[a]

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Entry

DESs

Time [h]

Temp. [oC]

Yield[b]

1

-

5

40

nd[c]

2

ChCl/glycerol

5

40

20

3

ChCl/ethylene glycol

5

40

10

4

ChCl/benzoic acid

5

40

12

5

ChCl/urea

5

40

49

6

ChCl/urea

5

50

76

7

ChCl/urea

5

60

85

8

ChCl/urea

5

70

89

9[d]

ChCl/urea

3

70

93

10[e]

ChCl/urea

2

70

98

11[f]

ChCl/urea

2

70

97

Reaction conditions: N-benzyl spiro-epoxyoxindole 1a [0.2 mmol], CO2 [1 atm, Balloon],

ChCl/urea [100 mg]. detected.

[d]

[b]

Yield of isolated product after column chromatography.

[c]

nd = Not

ChCl/urea [200 mg]. [e]ChCl/urea [300 mg]. [f]Reaction conducted at 2.5 mmol scale

using ChCl/urea [300 mg]. On the basis of these studies, we optimized the reaction parameters and consequently substrate scope was investigated and the results are shown in Table 2. The system appears to be tolerant towards electronic demands and variety of N-protected spiro-epoxy oxindoles 1a-10a resulted in good to excellent yields [67-98%]. Experiments to probe the effect of Nprotection on the spiro-epoxy oxindoles (1a-3a) did not affect the efficiency of the reaction and produced the corresponding products in short reaction time [Table 2, 1b-3b]. In contrast, inclusion of substitutions in the aromatic ring derived substrates required slightly longer reaction time [6-8 h] for achieving good yield [Table 2, 4b-10b]. At the present stage of investigation, we could not extend the substrate scope to include internal epoxides, since we observed no conversion under the optimized reaction conditions. This is due to the steric


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factor involved with these substrates and generally this kind of substrate requires high pressure and temperature to achieve better conversion.57-60 Apart from this, all the products were characterized with 1H and 13C NMR spectroscopy, FT-IR and GC-MS techniques and included in the supporting information [Figure S1 – S60]. Table 2. Substrate scope for the cycloaddition reaction of spiro-epoxy oxindoles with CO2.[a]

[a]

Conditions: Spiro-epoxy oxindoles [0.2 mmol], ChCl/urea [300 mg], 1 atm CO2. [b]Isolated

yield after flash chromatography.



Delighted with the activity of DES in spiro-cyclic carbonate formation, furthermore we speculated to demonstrate the scale-up reaction at 2.5 mmol scale under the optimized protocol and the reaction was completed in 2 h with 97% conversion [Table 1, entry 11]. We also calculated Sheldon E-factor of the whole process and the value obtained [0.40] indicates the greenness of the protocol61-63 [please see supporting information]. It is very important for a new molecule to confirm their structure with single crystal XRD analysis, thereby we solved the structure of spiro-cyclic carbonate,64 2b which also confirms the feasibility of the reaction [Figure 2].

Figure 2. Thermal ellipsoid plot of the spiro-cyclic carbonate 2b with atom numbering scheme [50% probability factor for the thermal ellipsoids]. The reaction mechanism for the DES based cyclic carbonate formation is wellestablished.40 With the understanding from the literature and based on the results obtained, the basic steps involved in the spiro-cyclic carbonate formation are depicted in [Figure 3]. It shows that the polarization of spiro-epoxy C-O bond through H-bonding and the subsequent nucleophilic attack of chloride anion resulted in the ring-opening of epoxide.


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This occurs due to the synergetic effect of choline chloride and urea. Then, the ring-opened intermediate further reacts with CO2 to form the corresponding cyclic carbonate and regenerate the DES.

Figure 3: Probable mechanism for the formation of spiro-cyclic carbonate. Recyclability After completion of the reaction, the reaction mass was partitioned with 2-methyl tetrahydrofuran and water in equimolar ratio. The reaction mass was then stirred for 5 minutes so that the organic part gets completely dissolved. The water layer was then separated from organic layer and extracted thrice [10 mL] with 2-methyl tetrahydrofuran. Subsequently, the water layer was evaporated and dried overnight in vacuum to yield



recycled ChCl:urea DES for next run and could be effectively used for 4 cycles with consistent yield [Figure 4].

Figure 4. Recyclability studies of ChCl:urea DES in the spiro-cyclic carbonate formation.

Conclusion In summary, we have disclosed the strategy for the synthesis of spiro-cyclic carbonate from spiro epoxy oxindoles. The advantage of this protocol involves the use of deep eutectic solvent ChCl/urea as a green media, co-catalyst free and mild reaction conditions for the synthesis of different substituted spiro-cyclic carbonate in good to excellent yields. The developed protocol is scalable and also allow a modular synthesis, thus providing a platform to access similar structure. We believe that this newly introduced cyclic carbonate should enable new directions and have a broad applicability. Evaluation of other properties of these spiro-cyclic carbonate are currently under investigation in our laboratory. Associated Content Supporting Information


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Copies of 1H NMR/13C NMR and characterisation data for new compounds. This material is available free of charge via the Internet at http://pubs.acs.org. Author Information Corresponding Author *Email: [email protected], [email protected] Notes The authors declare no competing financial interest. Acknowledgement [CSMCRI Communication No. 109/2018], RT and RIK are thankful to UGC and HCP0009 for financial assistance. SS sincerely thank DST for the DST-INSPIRE Faculty award [DST/INSPIRE/04-I/2017/000003]. RT is thankful to AcSIR for Ph.D. registration. The authors are also thankful to Analytical and Environment Science Division and Centralized Instrument Facilities for providing instrumental facilities.

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Table of Contents

Synopsis The cycloaddition reaction of spiro-epoxyoxindoles with CO2 [balloon] has been demonstrated using DESs under milder conditions to afford spiro-cyclic carbonates in excellent yields [up to 98%].


Cycloaddition reaction of spiro-epoxy oxindole with CO2 at

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