Ag(I)-Catalyzed Cascade Reaction of Sulfonylhydrazone with

Letter Cite This: Org. Lett. 2018, 20, 2204−2207

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Cu(II)/Ag(I)-Catalyzed Cascade Reaction of Sulfonylhydrazone with Anthranils: Synthesis of 2‑Aryl-3-sulfonyl Substituted Quinoline Derivatives Fei Wang, Pei Xu, Shun-Yi Wang,* and Shun-Jun Ji* Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215123, China S Supporting Information *

ABSTRACT: In this paper, a Cu(II)/Ag(I)-catalyzed cascade reaction of anthranils with sulfonylhydrazone to construct 2-phenyl-3-sulfonyl disubstituted quinoline derivatives under mild conditions was studied. The mechanism study indicated that this reaction involves radical addition, and new C−C, C−N, and C− S bonds were constructed in one step.

Q

uinoline derivatives are one of the most important heterocyclic compounds, widely found in natural products, drug-related molecules, and functional materials.1 Functionalized quinoline plays an important role in antimalaria, inflammation treatment, antiasthma, antibacterial, and antiallergy.2 In recent years, the synthesis of quinoline has been greatly developed. However, most of the existing methods require highly functionalized starting materials promoted by expensive transition metals, and the reaction conditions are mostly harsh.3,4 The methods for the synthesis of 2,3disubstituted quinoline with potential activities are still rare. Therefore, it is more desirable to develop a green and efficient protocol to prepare 2,3-disubstituted quinolone under mild conditions. In recent years, anthranil has been widely used for its unique electronic properties as a multifunctional synthesis intermediate. Various transition metal catalyzed reactions of anthranil with new C−C and C−N bond formations to construct indole,5 quinoline,6 pyrazole,7 pyrrole,8 and other nitrogen-containing heterocyclic compounds have been well studied (Figure1, eq 1). For example, Prof. Li’s, Jiao’s, and other research groups have reported the rhodium-catalyzed reactions of anthranil applied to the synthesis of quinoline derivatives.6b−g

Hydrazone derivatives are a class of important organic intermediates for the construction of complex molesulces.9 In the past few years, great progress has been made in the reaction of hydrazones catalyzed by transition metals, including the insertion reaction of X−H (X = C, Si, N, O, etc.),10 cyclization,11 1,2-migration,12 and so on. In recent years, the reaction of p-toluenesulfonyl hydrazone under the action of a copper catalyst has also become a hot topic. The reaction generally proceeds through two processes (sulfonyl free radical13 or sulfonyl anion14) (Figure1, eq 2). In view of the unique reaction characteristics of anthranil and p-toluenesulfonyl hydrazone, herein, we describe a Cu(II)/Ag(I)-catalyzed cascade reaction of anthranils with sulfonylhydrazone to construct 2-phenyl-3-sulfonyl disubstituted quinoline derivatives under mild conditions (Figure 1, eq 3). Initially, we attempted the reaction of anthranil 1a, ptoluenesulfonyl hydrazine 2a, copper acetate (15 mol %), and AgOTf (10 mol %) in DCE at 110 °C for 12 h. Gratifyingly, the reaction proceeded smoothly to give the 2-phenyl-3-sulfonyl substituted quinoline 3a in 46% isolated yield (Table 1, entry 1). The reaction failed to afford 3a without a copper catalyst (Table 1, entry 2). Other copper catalysts, such as Cu(NO3)2 and CuCl, resulted in 3a in 30% and 40% yields, respectively (Table 1, entries 3 and 4). Then, we studied the effects of the silver additives such as AgNO3, Ag2CO3, and AgSbF6, which afforded 3a in 37−43% yields (Table 1, entries 6−8). The reaction failed to afford 3a without a silver additive (Table 1, entry 5). We also examined the amount of AgOTf. Increasing or decreasing the amount of AgOTf did not have a significant effect on the yield of 3a (Table 1, entries 9−10). In order to improve the yields of 3a, other ligands such as PPh3 and Xphos were added to the reaction system. Unfortunately, no better results were obtained (Table 1, entries 11−12). We screened the solvents such as were investigated, of which no better result was obtained. We also screened several solvents and found that

Figure 1. Reactions of anthranil and tosylhydrazone.

Received: February 13, 2018 Published: April 4, 2018

© 2018 American Chemical Society

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DOI: 10.1021/acs.orglett.8b00525 Org. Lett. 2018, 20, 2204−2207

Letter

Organic Letters Table 1. Optimization of the Reaction Conditionsa

Scheme 1. Substrate Scopea,b

entry

Cu (mol %)

Ag (mol %)

solvent

yield (%)b

1 2 3 4 5 6 7 8 9 10 11c 12d 13 14 15 16 17e 18f

Cu(OAc)2 (15) − Cu(NO)2 (15) CuCl (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15) Cu(OAc)2 (15)

AgOTf (10) AgOTf (10) AgOTf (10) AgOTf (10) − AgNO3 (10) Ag2CO3 (10) AgSbF6 (10) AgOTf (20) AgOTf (30) AgOTf (10) AgOTf (10) AgOTf (10) AgOTf (10) AgOTf (10) AgOTf (10) AgOTf (10) AgOTf (10)

DCE DCE DCE DCE DCE DCE DCE DCE DCE DCE DCE DCE MeCN dioxane DMF xylene DCE DCE

46 n.r. 30 40 trace 37 43 40 44 47 46 46 38 35 20 n.r 46 46

a

Reaction conditions: 1a (0.6 mmol), 2a (0.3 mmol), copper catalyst, solvent (3 mL), Ag.additive. 110 °C, 12 h. bIsolated yields. cPPh3 (0.03 mmol) was used as ligand. dXphos (0.03 mmol) was used as as ligand. e Under N2 atmosphere. fUnder Ar atmosphere.

a

Reaction conditions: anthranils 1a (0.6 mmol), substituted sulfonylhydrazone 2 (0.3 mmol), Cu(OAc)2 (0.045 mmol), AgOTf (0.03 mol) in DCE (3 mL), 110 °C. bIsolated yields.

acetonitrile (MeCN), 1,4-dioxane, and DMF did not give better results (Table 1, entries 13−16). The reaction in xylene even failed to afford 3a. The reaction under s nitrogen or an argon atmosphere had no effects on the yield of 3a (Table 1, entries 17−18). Therefore, the optimized reaction conditions are the following: anthranil 1 (2.0 equiv), p-toluenesulfonyl hydrazine 2 (1.0 equiv), Cu(OAc)2 (15 mol %), and AgOTf (10 mol %) in 3 mL of DCE at 110 °C. With the optimum conditions in hand, we first studied the scope of p-toluenesulfonylhydrazones bearing different aromatic rings (Scheme 1). It was found that there is a slight increase in the reaction yields when the substrates’ benzene ring bears electron-donating groups. The target products 3b−d were obtained in 49−66% yields. The reaction of 1a with para tertbutyl substituted N′-(1-(4-(tert-butyl)phenyl)ethylidene)-4methylbenzenesulfonohydrazide 2e furnished the desired product 3e in 53% yield. The reaction of 1a with para-phenyl p-toluenesulfonylhydrazone 2f could lead to the desired product 3f in 46% yields. When p-toluenesulfonylhydrazones bearing electron-withdrawing groups were applied to the reactions, similar yields were observed. The ester and sulfone substituted p-toluenesulfonylhydrazone 2h and 2i resulted in the desired products 3h and 3i in 46% and 48% yields, respectively. The reactions of β-naphthalene and α-naphthalene functionalized p-toluenesulfonylhydrazones afforded the desired products 3l and 3m in 60% and 47% yields, respectively. Unfortunately, the reactions of heterocycle-functionalized ptoluenesulfonylhydrazones 2n−p failed to give the desired products 3n−p. When the N′-(3,3-dimethylbutan-2-ylidene)-4methylbenzenesulfonohydrazide 2r was subjected to the reaction with 1a, it was found that N′-(3,3-dimethylbutan-2ylidene)-4-methyl-N-tosylbenzenesulfonohydrazide 3r′ was observed in 37% yield instead of quinoline product 3r. This may be due to the lower reactivity of alkylhydrazone 2r and the

corresponding intermediate’s inability to further react with benzisoxazole. Next, we examined the reactions of 1a with sulfonohydrazides bearing different substituents on the sulfonylbenzene ring (Scheme 2). It was found that the reaction of N′-(1Scheme 2. Substrate Scopea,b

a

Reaction conditions: anthranils 1 (0.6 mmol), substituted sulfonylhydrazone 2 (0.3 mmol), Cu(OAc)2 (0.045 mmol), AgOTf (0.03 mmol) in DCE (3 mL), 110 °C. bIsolated yields.

phenylethylidene)benzenesulfonohydrazide with 1a gave the desired product 4a in 42% yield. Weak electron-withdrawing groups, such as CN and Br substituted sulfonohydrazides 2c and 2d, could also lead to the desired products 4b and 4c in 51% and 47 yields, respectively. The reaction of N′-(1phenylethylidene)pyridine-4-sulfonohydrazide 2e could also gave the desired product 4d in 27% yield after 48 h. 2205

DOI: 10.1021/acs.orglett.8b00525 Org. Lett. 2018, 20, 2204−2207

Letter

Organic Letters

Scheme 5. First, p-toluenesulfonyl hydrazone 2a reacts with zwitterion 1a′ generated from anthranil 1a to give (1-

Then, we investigated the reaction scope of benzo[c]isoxazoles under the optimized reaction conditions (Scheme 2). The reaction of [1,3]dioxolo[4′,5′:4,5]benzo[1,2-c]isoxazole 1b with 2a furnished the desried product 4e in 45% yield. The reactions of 5-methoxybenzo[c]isoxazole and 6-methoxybenzo[c]isoxazole afforded the desired products 4f and 4g in 40% and 60% yields, respectively. When 6-bromobenzo[c]isoxazole was subjected to the reaction with 2c, 4h could be obtained in 47% yield. To demonstrate the application of our method in organic synthesis, we tried the scale-up reaction of benzo[c]isoxazole 1a with 4-methyl-N′-(1-(p-tolyl)ethylidene)benzenesulfonohydrazide 2d under the standard reaction conditions. To our delight, the desired product 3d could be obtained in 55% yield (Scheme 3).

Scheme 5. Plausible Reaction Mechanism

Scheme 3. Scale-up Reaction of 1a and 2d

diazoethyl)benzene A and sulfonyl radical. Cu(II) attacks A to furnish copper carbene B with release of N2. 1a coordinates to B to afford C. Following carbene migratory insertion of C, D is formed. Then, the ring opening of D via N−O bond cleavage generates intermediates E and its corresponding tautomer F. AgOTf promoted cyclization of F can give the side product 3a′. The sulfonyl radical reacts with F to lead to G. AgOTf promoted cyclization of G affords the main product 3a. In summary, we developed a Cu(II)/Ag(I)-catalyzed domino reaction of p-toluenesulfonylhydrazone with anthranils to construct 2,3-disubstituted quinoline derivatives in one step via free-radical cyclization. New C−C, C−N, and C−S bonds were established in this reaction, which provided a practical method for the preparation of 2,3-disubstituted quinolines.

In order to further understand the reaction mechanism, we conducted a series of control experiments (Scheme 4). When 1 Scheme 4. Control Experiments

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.orglett.8b00525. Detailed experimental procedures and characterization datum (PDF)

equiv of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) was added to the reaction system of 1a with 2d, the yield of 3d reduced to only 16%. At the same time, the decomposed product 1a′ and quinoline product 5a were isolated in 24% and 33% yields, respectively (Scheme 4, eq 1). When 1 equiv of another radical scavenger (1,1-diphenylethylene) was added to the reaction system of 1a with 2d, it was found that the desired product 3d was obtained in 35% yield with the detection of radical trapped product 3d′ by LC-MS (Scheme 4, eq 2). These results indicated that the reaction involves a Ts radical process. Next, we attempted the control experiment of 1a and 2i with 6a under the optimized conditions. It was found that only 3i was obtained in 48% yield without the formation of 3a (Scheme 4, eq 3). A further control experiment of 6a with p-toluenesulfonylhydrazide as the source of Ts radical failed to give 3a (Scheme 4, eq 4). These results meant that the Ts radical has been involved in the reaction before the formation of the quinoline skeleton. Based on the above experimental results and the literature reports,15 we proposed a plausible reaction mechanism in

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Shun-Yi Wang: 0000-0002-8985-8753 Shun-Jun Ji: 0000-0002-4299-3528 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We gratefully acknowledge the National Natural Science Foundation of China (21772137, 21672157, 21372174), the Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (No. 2206

DOI: 10.1021/acs.orglett.8b00525 Org. Lett. 2018, 20, 2204−2207

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Organic Letters

Wei, Q.; Liu, F.-L.; Deng, Q.-H.; Beauchemin, A. M.; Xiao, W.-J. Angew. Chem., Int. Ed. 2014, 53, 12163. (c) Zhou, Z.; Liu, Y.; Chen, J.F.; Yao, E.; Cheng, J. Org. Lett. 2016, 18, 5268. (d) Li, L.-X.; Liu, P.-P.; Su, Y.-J.; Huang, H.-M. Org. Lett. 2016, 18, 5736. (e) Punner, F.; Sohtome, Y.; Sodeoka, M. Chem. Commun. 2016, 52, 14093. (f) Zhao, Q.-Q.; Chen, J.; Yan, D.-M.; Chen, J.-R.; Xiao, W.-J. Org. Lett. 2017, 19, 3620. (g) Chen, M.-M.; Wang, L.-J.; Ren, P.-X.; Hou, X.-Y.; Fang, Z.; Han, M.-N.; Li, W. Org. Lett. 2018, 20, 510. (12) (a) Bruneau, C. Angew. Chem., Int. Ed. 2005, 44, 2328. (b) Marco- Contelles, J.; Soriano, E. Chem. - Eur. J. 2007, 13, 1350. (c) Marion, N.; Nolan, S. P. Angew. Chem., Int. Ed. 2007, 46, 2750. (d) Zhang, Y.; Wang, J.-B. Eur. J. Org. Chem. 2011, 2011, 1015. (13) Mao, S.; Gao, Y.-R.; Zhu, X.-Q.; Guo, D.-D.; Wang, Y.-Q. Org. Lett. 2015, 17, 1692−1695. (14) Zheng, Y.; Qiu, L.-H.; Hong, K.-M.; Dong, S.-L.; Xu, X.-F. Chem. - Eur. J. 2017, DOI: 10.1002/chem.201704759. (15) (a) Xia, Y.; Qiu, D.; Wang, J.-B. Chem. Rev. 2017, 117, 13810. (b) Liu, Z.-X.; Wang, J.-B. J. Org. Chem. 2013, 78, 10024.

16KJA150002), the Ph.D. Programs Foundation of PAPD, the project of scientific and technologic infrastructure of Suzhou (SZS201708), and Soochow University for financial support. We thank Qin Yuan and Rong Zhang (Soochow University) for reproducing the results of 3a, 3c, 4a, and 4d.

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REFERENCES

(1) (a) El Sayed, K. E.; Al-Said, M. S.; El-Feraly, F. S.; Ross, S. A. J. Nat. Prod. 2000, 63, 995. (b) Cretton, S.; Breant, L.; Pourrez, L.; Ambuehl, C.; Marcourt, L.; Ebrahimi, S. N.; Hamburger, M.; Perozzo, R.; Karimou, S.; Kaiser, M.; Cuendet, M.; Christen, P. J. Nat. Prod. 2014, 77, 2304. (c) Michael, J. P. Nat. Prod. Rep. 2008, 25, 166. (d) Solomon, V. R.; Lee, H. Curr. Med. Chem. 2011, 18, 1488. (e) Kwon, J. E.; Park, S. Y. Adv. Mater. 2011, 23, 3615. (f) Dibble, D. J.; Park, Y. S.; Mazaheripour, A.; Umerani, M. J.; Ziller, J. W.; Gorodetsky, A. A. Angew. Chem., Int. Ed. 2015, 54, 5883. (2) (a) Michael, J. P. Nat. Prod. Rep. 2007, 24, 223. (b) Michael, J. P. Nat. Prod. Rep. 2005, 22, 627. (c) Roma, G.; Di Braccio, M.; Grossi, G.; Mattioli, F.; Ghia, M. Eur. J. Med. Chem. 2000, 35, 1021. (d) Chen, Y. L.; Fang, K. C.; Sheu, J. Y.; Hsu, S. L.; Tzeng, C. C. J. Med. Chem. 2001, 44, 2374. (3) (a) Xu, P.; Zhu, T.-H.; Wei, T.-H.; Wang, S.-Y.; Ji, S.-J. RSC Adv. 2016, 6, 32467. (b) Marco-Contelles, J.; Mayoral, E. P.; Samadi, A.; Carreiras, M. d. C.; Soriano, E. Chem. Rev. 2009, 109, 2652. (c) Willumstad, T. P.; Boudreau, P. D.; Danheiser, R. L. J. Org. Chem. 2015, 80, 11794. (d) Kong, L.-K.; Zhou, Y.-Y.; Huang, H.; Yang, Y.; Liu, Y.-Y.; Li, Y. Z. J. Org. Chem. 2015, 80, 1275. (4) (a) Rehan, M.; Hazra, G.; Ghorai, P. Org. Lett. 2015, 17, 1668. (b) An, X.-D.; Yu, S.-Y. Org. Lett. 2015, 17, 2692. (c) Liu, G.-Y.; Yi, M.-C.; Liu, L.; Wang, J.-J.; Wang, J.-H. Chem. Commun. 2015, 51, 2911. (5) Jin, H.-M.; Huang, L.; Xie, J.; Rudolph, M.; Rominger, F.; Hashmi, A. S. K. Angew. Chem., Int. Ed. 2016, 55, 794; Angew. Chem. 2016, 128, 804. (6) (a) Jin, H.-M.; Tian, B.; Song, X.-L.; Xie, J.; Rudolph, M.; Rominger, F.; Hashmi, A. S. K. Angew. Chem., Int. Ed. 2016, 55, 12688. (b) Yu, S.-J.; Tang, G.-D.; Li, Y.-Z.; Zhou, X.-K.; Lan, Y.; Li, X.-W. Angew. Chem., Int. Ed. 2016, 55, 8696. (c) Zou, M.-C.; Liu, J.-Z.; Tang, C.-H.; Jiao, N. Org. Lett. 2016, 18, 3030. (d) Yu, S.-J.; Li, Y.-Y.; Zhou, X.-K.; Wang, H.; Kong, L.-H.; Li, X.-W. Org. Lett. 2016, 18, 2812. (e) Tang, C.-H.; Zou, M.-C.; Liu, J.-Z.; Wen, X.-J.; Sun, X.; Zhang, Y.Q.; Jiao, N. Chem. - Eur. J. 2016, 22, 11165. (f) Li, H.-Y.; Jie, J.-Y.; Wu, S.-X.; Yang, X.-B.; Xu, H. Org. Chem. Front. 2017, 4, 250. (g) Shi, L.-L.; Wang, B.-Q. Org. Lett. 2016, 18, 2820. (h) Tiwari, D. K.; Phanindrudu, M.; Wakade, S. B.; Nanubolu, J. B.; Tiwari, D. K. Chem. Commun. 2017, 53, 5302. (7) Li, L.; Wang, H.; Yu, S.-J.; Yang, X.-F.; Li, X.-W. Org. Lett. 2016, 18, 3662. (8) (a) Lei, X.-Q.; Li, L.-B.; He, Y.-P.; Tang, Y.-F. Org. Lett. 2015, 17, 5224. (b) Pusch, S.; Kowalczyk, D.; Opatz, T. J. Org. Chem. 2016, 81, 4170. (c) Zhou, A.-H.; He, Q.; Shu, C.; Yu, Y.-F.; Liu, S.; Zhao, T.; Zhang, W.; Lu, X.; Ye, L.-W. Chem. Sci. 2015, 6, 1265. (9) (a) Kishner, N. Zh. Russ. Fiz.-Khim. O-va., Chast. Khim 1911, 43, 582. (b) Wolff, L. Justus Liebigs Ann. Chem. 1912, 394, 86. (10) (a) Zhu, C.-L.; Chen, P.-Q.; Wu, W.-Q.; Qi, C.-R.; Ren, Y.-W.; Jiang, H.-F. Org. Lett. 2016, 18, 4008. (b) Zhu, C.-L.; Li, J.-W.; Chen, P.-Q.; Wu, W.-Q.; Ren, Y.-W.; Jiang, H.-F. Org. Lett. 2016, 18, 1470. (c) Wu, X.-X.; Shen, Y.; Chen, W.-L.; Chen, S.; Hao, X.-H.; Xia, Y.; Xu, P.-F.; Liang, Y.-M. Chem. Commun. 2015, 51, 8031. (d) Wu, X.-X.; Zhou, P.-X.; Wang, L.-J.; Xu, P.-F.; Liang, Y.-M. Chem. Commun. 2014, 50, 3882. (e) Huang, Y.-B.; Li, X.-W.; Yu, Y.; Zhu, C.-L.; Wu, W.-Q.; Jiang, H.-F. J. Org. Chem. 2016, 81, 5014. (f) Li, X.-W.; Liu, X.-H.; Chen, H.-J.; Wu, W.-Q.; Qi, C.-R.; Jiang, H.-F. Angew. Chem., Int. Ed. 2014, 53, 14485. (g) Barluenga, J.; Moriel, P.; Valdes, C.; Aznar, F. Angew. Chem., Int. Ed. 2007, 46, 5587. (h) Tian, M.-M.; Shi, X.-N.; Zhang, X.-Y.; Fan, X.-S. J. Org. Chem. 2017, 82, 7363. (11) (a) Chen, Z.-K.; Yan, Q.-Q.; Liu, Z.-X.; Xu, Y.-M.; Zhang, Y.-H. Angew. Chem., Int. Ed. 2013, 52, 13324. (b) Hu, X.-Q.; Chen, J.-R.; 2207

DOI: 10.1021/acs.orglett.8b00525 Org. Lett. 2018, 20, 2204−2207