Research Article Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
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Waste-Minimized Protocol for the Synthesis of Sulfonylated N‑Heteroaromatics in Water Long-Yong Xie,† Sha Peng,† Jia-Xi Tan,† Rong-Xia Sun,† Xianyong Yu,‡ Ning-Ning Dai,‡ Zi-Long Tang,‡ Xinhua Xu,§ and Wei-Min He*,†,§ †
Department of Chemistry, Hunan University of Science and Engineering, Yangzi Tang Road No. 130, Yongzhou 425100, China Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, Hunan University of Science and Technology, Taoyuan Roand No. 9, Xiangtan 411201, China § State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Lushan Road No.1, Changsha 410082, China ACS Sustainable Chem. Eng. Downloaded from pubs.acs.org by UNIV OF TASMANIA on 10/30/18. For personal use only.
‡
S Supporting Information *
ABSTRACT: An ecofriendly and practical method for the efficient synthesis of various sulfonylated N-heteroaromatics in water under metal-free, organic-solvent-free, neutral, and mild reaction conditions was developed. The employment of readily available reagents, wide substrate scope, high chemoselectivity, and regioselectivity make this protocol very practical. Importantly, the pure products can be easily obtained via filtration and washing by alcohol without extraction and recrystallization. KEYWORDS: In water, Sulfonyl chlorides, Sulfonylation, Sulfonylated N-heteroaromatics, Metal-free
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INTRODUCTION The development of step- and atom-economical aqueous organic reactions1−24 that can be conducted under neutral, metal-free, and mild reaction conditions in which the desired products can be obtained after the reaction through simple filtration without organic solvent extraction and recrystallization is one of the important targets in green chemistry. Over the past decades, the achievement of general and efficient protocols for the synthesis of sulfonylated N-heteroaromatics has attracted extensive attention of organic chemists because they have a wide range of applications in organic synthesis, pharmaceuticals, and functionalized material science.25−27 Thus, tremendous efforts have been dedicated to construct such motifs. Generally, the methodologies for the synthesis of sulfonylated N-heteroaromatics can be divided into two categories according to the reaction substrates: those that utilize heteroaromatic N-oxide substrates28−38 and those that functionalize the halogenated or sulfonate N-heteroaromatics.39−44 Both protocols continue to find widespread use, but they also have inevitable limitations. The limitation of sulfonylation45−58 of N-heteroaromatic N-oxides is that the functionalization occurs at the 2-position, but a competing reaction at the other position is often observed, especially in the case of isoquinolines33−36 and six-membered heteroaromatic N-oxides. The major advantage of the functionalization of halogenated or sulfonate N-heteroaromatics is the specific completely controllable regioselectivity. Since the first examples of Pd2(dba)3-catalyzed coupling of 2-bromopyridine with sodium p-toluenesulfinate in the presence of Cs2CO3 in toluene reported by Cacchi in 2004,39 considerable progress has been achieved over the past years.40−43 However, all of these protocols have the need for environmentally unfriendly © XXXX American Chemical Society
transition metal catalysts and (super)stoichiometric amount of bases to facilitate this transformation (Scheme 1a). In 2011, Scheme 1. Synthesis of Sulfonylated N-Heteroaromatics
Maloney and Kuethe developed a metal-free nucleophilic SNAr reaction for the synthesis of sulfonylated N-heteroaromatics from halogenated N-heteroaromatics and sodium sulfinate salts (Scheme 1b).44 All of the methods mentioned above can regioselectively construct the desired sulfonylated N-heteroaromatics, but these reactions are conducted in harmful Received: August 29, 2018 Revised: October 2, 2018
A
DOI: 10.1021/acssuschemeng.8b04339 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
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ACS Sustainable Chemistry & Engineering
Table 1. Optimization of Reaction Conditionsa
organic solvent59 at high reaction temperature with long reaction time. In addition, the sodium sulfonate salts have very limited commercial availability for aryl and alkyl variants and are often prepared from the corresponding sulfonyl chlorides under alkaline conditions.34 Cumbersome isolation and purification steps are necessary with the generation of significant amounts of chemical wastes and cause high cost of the terminal products. Coupled with environmental and economic concerns, the development of greener organic synthetic reactions from nontoxic, inexpensive, readily available, and ecofriendly raw materials is extremely attractive and essential. Very recently, metal-free sulfonylation of halogenate Oheterocycles with sodium sulfinates in 1,2-dichloroethane/H2O was reported by Wang (Scheme 1c).19 However, the scope of O-heteroaromatics was limited to activated 3,4-dihalo-2(5H)furanones, and the use of toxic chlorinated solvent is not avoided. To the best of our knowledge, no example of metalfree sulfonylation of halogenate N-heteroaromatics in water exists. As part of our ongoing interest in green organic synthesis,60−66 we have reported the ecofriendly synthesis of N-heteroaromatic derivatives.67−69 In this paper, we report for the first time a step- and atom-economical method for the efficient synthesis of various sulfonylated N-heteroaromatics from readily available halogenated or sulfonate N-heteroaromatics and sulfonyl chlorides in water under metal-free, organic-solvent-free, neutral, and mild reaction conditions (Scheme 1d). Notably, the pure sulfonylated products can be easily obtained by filtration and washing with alcohol without extraction and recrystallization.
entry
equiv of 2a
Na2SO3
solvent
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.5 1.0 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2
1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.5 1.0 1.3 1.3 1.3 1.3 1.3 1.3
H2O (1 mL) EtOH (1 mL) THF (1 mL) MeCN (1 mL) DCE (1 mL) DMF (1 mL) DMSO (1 mL) DMAC (1 mL) H2O (1 mL) H2O (1 mL) H2O (1 mL) H2O (1 mL) H2O (1.5 mL) H2O (0.5 mL) H2O (1 mL) H2O (1 mL) H2O (1 mL) H2O (1 mL)
19 20
1.2 1.2
1.3
H2O (1 mL) H2O (1 mL)
conditions 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 80 °C, 2 h 100 °C, 2 h 120 °C, 2 h 60 °C, 2 h ultrasound, 20 min 80 °C, 1.5 h 60 °C, 2 h
yieldb 91% trace trace N.R.c N.R. N.R. N.R. N.R. 92% 86% 93% 80% 91% 82% 87% 88% 61% 85% 76% N.R.
a Unless otherwise specified, the reactions were carried out in a vial in the presence of 1a (0.3 mmol), 2a, Na2SO3, and solvent (1 mL). b Estimated by 1H NMR using diethyl phthalate as internal reference. c N.R.: no reaction.
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RESULTS AND DISCUSSION Initially, the reaction of 2-chloroquinoline (1a) with tosyl chloride (2a) was selected as a model reaction to optimize various reaction parameters. To our delight, treatment of the 1a, 2a, and Na2SO3 in water at 80 °C for 2 h could produce the desired 2-sulfonylquinoline (3aa) in 91% yield. Notably, the insoluble sulfonylquinoline can be simply isolated via filtration, and the developed process can avoid the traditional organic solvent extraction. Either no formation or a trace amount of product was observed in organic solvents (entries 2−8). Further efforts in varying the loading of 2a, Na2SO3, water, as well as the reaction temperature did not provide improved efficiency of the coupling reaction (entries 9−17). No improvement in the developed transformation was observed when ultrasound irradiation was used instead of magnetic stirring (entry 18). Performing the reaction with 1.5 h, 18% of 1a was unreactive (entry 19). A control experiment in the absence of Na2SO3 gave no desired product, indicating that Na2SO3 is essential (entry 20). Aqueous media, neutral pH (7.1), metal- and base-free conditions, mild reaction temperature, operational simplicity, and excellent yield make this reaction an alternative method for the straightforward preparation of numerous sulfonylated N-heteroaromatics. With the optimized conditions in hand, we first investigated the substrate scope of benzenesulfonyl chlorides with 2chloroquinoline (1a) under the reaction conditions shown in entry 1 of Table 1. To our delight, substituted benzenesulfonyl chlorides with a wide range of synthetically valuable functional groups underwent a coupling reaction to form the expected sulfonylquinolines in good to excellent yields (3aa−3as). Neither electronic effect nor steric factor of benzenesulfonyl chlorides had a significant influence on the efficiency of the
coupling reaction. Polycyclic and heteroaromatic substituted sulfonyl chlorides could also be transformed into the corresponding sulfonylated products (3at−3av) in excellent yields. The reaction of aliphatic sulfonyl chlorides proceeded well under the optimal reaction conditions and afforded the desired sulfonylquinolines in moderate yields (3aw−3ay). The efficient synthesis of various camphor derivatives has attracted much attention because they are found in many biological natural products and pharmacologically synthetic compounds. Pleasingly, the cheap camphorsulfonyl chloride participated in the coupling reaction efficiently to afford the desired novel camphor derivative (3az). When trifluoromethanesulfonyl chloride was used as the substrate, no reaction was observed. Next, the scope of this reaction (Table 2) with respect to halogenated N-heteroaromatic was investigated. A series of 2and 4-chloroquinolines containing valuable functional groups at the different positions all underwent a coupling reaction smoothly (3ba−3na). Remarkably, the reaction of dihalogenated quinolines (1d and 1g, and 1h and 1j−1m) led to the excellently chemoselective coupling reaction of the 2- or 4halogen of quinolones to provide the desired sulfonylquinolines, respectively, leaving the other halogen atom unreacted, and thus available for further transformations (3da and 3ga, and 3ha and 3ja−3ma). The present protocol could further be applied to 1-chloroisoquinoline, chloropyridines, and 2chlorothiazole, regioselectively generating the expected products in good yields (3oa−3ua). In addition, the bromo-, iodo-, and sulfonate-quinolones (1v−1x) smoothly underwent sulfonylation to provide the 2-sulfonylquinolines in excellent yield. The 3-chloroquinoline, 2-chloropyrimidine, 2-chloroimiB
DOI: 10.1021/acssuschemeng.8b04339 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
Research Article
ACS Sustainable Chemistry & Engineering Table 2. Reaction Scopea
substrates was increased to double. This novel protocol followed ecofriendly GAP chemistry (group-assistant-purification chemistry), which avoids conventional purification procedures such as organic solvent extraction, silica gel column chromatography, and recrystallization. This is in conformity with the first of the 12 principles of green chemistry, which is that it is better to prevent waste rather than to treat or clean up waste after it is formed. A series of control experiments were performed to provide some insight into the coupling reaction mechanism. In principle, a sulfonyl chloride can be slowly reduced by Na2SO3 in the absence of base to form a sodium sulfinate salt. When 2-chloroquinoline 1a reacted with sodium 4toluenesulfinate 4a in the presence of a catalytic amount of 4toluenesulfonic acid or HCl, 3aa was formed in 91% and 89% yields, respectively. A yield of 52% could also be detected without acid additive in water at 80 °C by prolonging the reaction time to 20 h (Scheme 3a).3,55 Taken together, these Scheme 3. Control Experiments
a All reactions were carried out in a vial in the presence of 1 (0.5 mmol), 2 (0.6 mmol), Na2SO3 (0.65 mmol), and H2O (2 mL), 80 °C; isolated yields are reported.
dazole, 2-chloroquinoline N-oxide, and 4-bromo-5-ethoxy2(5H)-furanone gave no desired product under the current reaction conditions. As an economic and efficient protocol, the scale-up and operational simplicity of the coupling reaction have great practical significance for the preparation of sulfonyl Nheteroaromatics in the academic laboratory, and even in industry. Thus, the different scale reactions 1a with 2a were carried out under the optimized reaction conditions. As shown in Scheme 2, the high-purity sulfonylated product 3aa can be simply obtained by filtration and washing with alcohol.70−73 In addition, no effect on the yield and selectivity of the large-scale synthesis appeared when the molar concentration of the
observations implied that the sodium sulfinate might be the possible reaction intermediate and clearly confirmed that the proton (in situ formed via hydrolysis of a catalytic amount of sulfonyl chloride and self-ionization of water) is pivotal for the success of this coupling reaction. Considering that this type of sulfonylation reaction may involve the thiosulfonate intermediate, we attempted to treat 2-chloroquinoline with thiosulfonate 4b under standard reaction conditions, but no product was observed (Scheme 3b). The result suggested that the present reaction did not involve the direct generation of the thiosulfonate intermediate step. When 2 equiv of radical scavenger (BHT and diphenylethylene) was added to the reaction mixture, the coupling reaction proceeded as normal (Scheme 3c−d). Finally, we performed the radical clock experiments. Starting with phenylethylene containing a typical radical clock cyclopropane moiety, no desired ring-opening product was detected (Scheme 3e−f). These results suggested
Scheme 2. Gram-Scale Synthesis of 3aa
C
DOI: 10.1021/acssuschemeng.8b04339 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
Research Article
ACS Sustainable Chemistry & Engineering Scheme 4. Plausible Mechanism
ORCID
that the free-radical pathway is not involved in the developed reaction.19,74 On the basis of the above-mentioned observations and related references,30,55 a probable reaction mechanism is depicted in Scheme 4. The coupling reaction starts by hydrolysis of a catalytic amount of sulfonyl chloride 2 and self-ionization of water3,55 in heating conditions to generate a proton, which reacts with 2-chloroquinoline 1 to form an activated quinoline intermediate A. Simultaneously, sulfonyl chloride 2 is reduced by Na2SO3 to produce a nucleophilic sulfonyl anion B, which attacks at the more electrophilic C2 position of quinoline to form an intermediate C. Finally, the intermediate C followed by deprotonation to afford the product 3. Pure water could promote the process through enhancing the proton transfer and stabilizing the intermediate A, presumably because of its polarity effects.
Wei-Min He: 0000-0002-9481-6697 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS We are grateful for financial support from the postfunded projects of Hunan University of Science and Engineering and the National Natural Science Foundation of China (21302048).
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CONCLUSIONS In conclusion, we have established an ecofriendly and practical protocol for the efficient synthesis of various sulfonylated Nheteroaromatics in water under metal-, organic-solvent-free, neutral, and mild reaction conditions. The developed protocol (a) proceeds well with a wide range of halogenate, sulfonate Nheteroaromatics, and sulfonyl chlorides; (b) is highly chemoselective and regioselective; and (c) tolerates various valuable functional groups. Importantly, the pure sulfonylated products can be simply obtained by filtration and washing with alcohol without organic solvent extraction and recrystallization. Given the readily available reagents and the simplicity of the operation, this scalability and sustainability of the present protocol are expected to be ideal for industrial processes.
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EXPERIMENTAL SECTION
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ASSOCIATED CONTENT
General Procedure for the Synthesis of Sulfonylated NHeteroaromatics. Halogenated N-heteroaromatics (0.5 mmol), H2O (2 mL), sulfonyl chloride (0.6 mmol), and Na2SO3 (0.65 mmol) were consecutively placed in a pressure tube, and then, the mixtures were heated to 80 °C. The progress of the reaction was monitored by TLC. The reaction typically took within 2 h. Upon completion, the reaction was cooled to room temperature and stood for 4 h, and then, the crude product was collected via filtration; it was further purified by column chromatography on silica gel to obtain sulfonylated N-heteroaromatics.
* Supporting Information S
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.8b04339. 1 H and 13C NMR spectra of 3 compounds (PDF)
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AUTHOR INFORMATION
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DOI: 10.1021/acssuschemeng.8b04339 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
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DOI: 10.1021/acssuschemeng.8b04339 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
Research Article
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DOI: 10.1021/acssuschemeng.8b04339 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
