Copper(II)-Promoted Oxidation/[3+2]Cycloaddition/Aromatization Cascade: Efficient Synthesis of Tetrasubstituted NH-Pyrrole from Chalcones and Iminodiacetates

Zhang-qi Lin; Chao-dong Li; Zi-chun Zhou; Shuai Xue; Jian-rong Gao; Qing Ye; Yu-jin Li

doi:10.1055/s-0039-1689972

Synlett, Table of Contents

Synlett 2019; 30(12): 1442-1446
DOI: 10.1055/s-0039-1689972

letter

Copper(II)-Promoted Oxidation/[3+2]Cycloaddition/Aromatization Cascade: Efficient Synthesis of Tetrasubstituted NH-Pyrrole from Chalcones and Iminodiacetates

Zhang-qi Lin

,

Chao-dong Li

,

Zi-chun Zhou

,

Shuai Xue

,

Jian-rong Gao

,

Qing Ye

,

Yu-jin Li*

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, P. R. of China Email: lyjzjut@zjut.edu.cn

› Author Affiliations

Abstract

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Abstract

A simple and highly efficient method for the preparation of tetrasubstituted NH-pyrrole from a wide range of chalcones and diethyl iminodiacetates via a Cu(OAc)₂-promoted oxidation/[3+2]cycloaddition/aromatization cascade reaction has been developed. This reaction proceeds through dehydrogenations, deamination, and oxidative cyclization, affording the corresponding products in good to excellent yields. This convenient methodology for constructing tetrasubstituted NH-pyrroles has several advantages over existing methods, such as the use of easily accessible chalcones and readily available diethyl iminodiacetates, and mild reaction conditions. A wide range of substrates are tolerated.

Key words

Cu(II)-promoted - tetrasubstituted NH-pyrrole - iminodiacetate - oxidation/[3+2] cycloaddition/aromatization - cascade reaction

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References

References and Notes

1a Jansen R, Sood S, Mohr KI, Kunze B, Irschik H, Stadler M, Müller R. J. Nat. Prod. 2014; 77: 2545
1b Liu R, Liu Y, Zhou YD, Nagle DG. J. Nat. Prod. 2007; 70: 1741
1c Grube A, Kock M. Org. Lett. 2006; 8: 4675
1d Colhoun HM, Betteridge DJ, Durrington PN, Hitman GA, Neil HA. W, Livingstone SJ, Thomason MJ, Mackness MI, Charlton-Menys V, Fuller JH. Lancet 2004; 364: 685
1e Lindel T, Breckle G, Hochgurtel M, Volk C, Grube A, Kock M. Tetrahedron Lett. 2004; 45: 8149
1f Fujita M, Nakao Y, Matsunaga S, Seiki M, Itoh Y, Van Yamashita J, Soest RW. M, Fusetani N. J. Am. Chem. Soc. 2003; 125: 15700
1g Furstner A. Angew. Chem. Int. Ed. 2003; 42: 3582

2 Fan H, Peng J, Hamann MT, Hu JF. Chem. Rev. 2008; 108: 264
3 Young IS, Thornton PD, Thompson A. Nat. Prod. Rep. 2010; 27: 1801

4a Frode R, Hinze C, Josten I, Schmidt B, Steffan B, Steglich W. Tetrahedron Lett. 1994; 35: 1689
4b Hashimoto T, Yasuda A, Akazawa K, Takaoka S, Tori M, Akazawa Y. Tetrahedron Lett. 1994; 35: 2559

5a Pongprom N, Bachitsch H, Bauchinger A, Ettefagh H, Haider T, Hofer M, Knafl H, Slanz R, Waismeyer M, Wieser F, Spreitzer H. Monatsh. Chem. 2010; 141: 53
5b Deblander J, Van Aeken S, Jacobs J, De Kimpe N, Tehrani KA. Eur. J. Org. Chem. 2009; 4882
5c Claessens S, Jacobs J, Van Aeken S, Tehrani KA, De Kimpe N. J. Org. Chem. 2008; 73: 7555
5d Matiychuk VS, Martyack RL, Obushak ND, Ostapiuk YV, Pidlypnyi NI. Chem. Heterocycl. Compd. 2004; 40: 1218
5e Frincke JM, Faulkner DJ. J. Am. Chem. Soc. 1982; 104: 265
5f Padwa A, Chen YY, Dent W, Nimmesgern H. J. Org. Chem. 1985; 50: 4006
5g Parker KA, Cohen ID, Padwa A, Dent W. Tetrahedron Lett. 1984; 25: 4917
5h Boven E, Erkelens CA. M. E, Luning M, Pinedo HM. Br. J. Cancer 1990; 61: 709

6a Estevez V, Villacampa M, Menendez JC. Chem. Commun. 2013; 49: 591
6b Kaupp G, Schmeyers J, Kuse A, Atfeh A. Angew. Chem. Int. Ed. 1999; 38: 2896

7a Madabhushi S, Vangipuram VS, ReddyMallu KK, Chinthala N, Beeram CR. Adv. Synth. Catal. 2012; 354: 1413
7b Schmidt EY, Mikhaleva AI, Vasil’tsov AM, Zaitsev AB, Zorina NV. ARKIVOC 2005; (vii): 11
7c Zaitsev AB, Schmidt EY, Mikhaleva AM, Afonin AV, Ushakov IA. Chem. Heterocycl. Compd. 2005; 41: 722
7d Vasil’tsov AM, Zaitsev AB, Schmidt EY, Mikhaleva AI, Afonin AV. Mendeleev Commun. 2001; 11: 74
7e Petrova OV, Mikhaleva AI, Sobenina LN, Schmidt EY, Kositsyna EI. Mendeleev Commun. 1997; 7: 162

8a Zelina EY, Nevolina TA, Sorotskaja LN, Skvortsov DA, Trushkov IV, Uchuskin MG. J. Org. Chem. 2018; 83: 11747
8b Han SZ, Zard SZ. Org. Lett. 2014; 16: 1992
8c Li P, Zhao JJ, Xia CG, Li FW. Org. Lett. 2014; 16: 5992
8d Ramírez-Rodríguez A, Méndez JM, Jiménez CC, León F, Vazquez A. Synthesis 2012; 44: 3321
8e Wang HY, Mueller DS, Sachwani RM, Kapadia R, Londino HN, Anderson LL. J. Org. Chem. 2011; 76: 3203
8f Aginagalde M, Bello T, Masdeu C, Vara Y, Arrieta A, Cossío FP. J. Org. Chem. 2010; 75: 7435
8g Chen JX, Wu HY, Zheng ZG, Jin C, Zhang XX, Sua WK. Tetrahedron Lett. 2006; 47: 383

9a Liu Y, Hu HY, Wang X, Zhi SJ, Kan YH, Wang C. J. Org. Chem. 2017; 82: 4194
9b Wu X, Geng X, Zhao PG, Zhang JJ, Wu YD, Wu AX. Chem. Commun. 2017; 53: 3438
9c Huang HM, Li YJ, Gao JR. J. Org. Chem. 2014; 79: 1084
9d Gothelf KV, Hazell RG, Jørgensen KA. J. Org. Chem. 1996; 61: 346
9e Huisgen R. Angew. Chem. 1963; 75: 604

10a Kotha S, Todeti S, Das T, Datta A. Tetrahedron Lett. 2018; 59: 1023
10b Hosseini-Sarvari M, Najafvand-Derikvandi S, Jarrahpour A, Heiran R. Chem. Hetrocycl. Comp. 2014; 49: 1732
10c Aydogan F, Yolacan C. J. Chem. 2013; 976724
10d Fang Y, Leysen D, Ottenheijm HC. J. Synth. Commun. 1995; 25: 1857
10e Clauson-Kaas N, Tyle Z. Acta Chem. Scand. 1952; 6: 667

11a Kirill IM, Galenko EE, Galenko AV, Novikov MS, Ivanov AY, Starova GL, Khlebnikov AF. J. Org. Chem. 2018; 83: 3177
11b Bhardwaj V, Gumber D, Abbot V, Dhiman S, Sharma P. RSC Adv. 2015; 5: 15233
11c Zhu L, Yu Y, Mao Z, Huang XL. Org. Lett. 2015; 17: 30
11d Chen GQ, Zhang XN, Wei Y, Tang XY, Shi M. Angew. Chem. Int. Ed. 2014; 53: 8492
11e Bauer I, Knolker H. Top. Curr. Chem. 2012; 309: 203
11f Chattopadhyay B, Gevorgyan V. Angew. Chem. Int. Ed. 2012; 51: 862

12a Cai Q, Li DK, Zhou RR, Shu WM, Wu YD, Wu AX. Org. Lett. 2016; 18: 1342
12b Gao P, Wang J, Bai ZJ, Shen LI, Yan YY, Yang DS, Fan MJ, Guan ZH. Org. Lett. 2016; 18: 6074
12c Galenko EE, Galenk AV, Khlebnikov AF, Novikov MS. RSC Adv. 2015; 5: 18172
12d Huang HM, Huang F, Li YJ, Jia JH, Ye Q, Han L, Gao JR. RSC Adv. 2014; 4: 27250
12e Saito A, Konishi O, Hanzawa Y. Org. Lett. 2010; 12: 372
12f Egi M, Azechi K, Akai S. Org. Lett. 2009; 11: 5002
12g Ackermann L, Sandmann R, Kaspar LT. Org. Lett. 2009; 11: 2031
12h Cacchi S, Fabrizi G, Filisti E. Org. Lett. 2008; 10: 2629

13a Li TF, Yan H, Li XC, Wang CX, Wan BS. J. Org. Chem. 2016; 81: 12031
13b Xiong MJ, Yu SS, Xie X, Li S, Liu YH. Organometallics 2015; 34: 5597
13c Boudriga S, Askri M, Rammah M, Monnier-Jobé K. J. Chem. Res. 2003; 208

14a Zhou NN, Li ZL, Xie ZX. Org. Chem. Front. 2015; 2: 1521
14b Zhou NN, Xie T, Liu L, Xie ZX. J. Org. Chem. 2014; 79: 6061

15a Huang HH, Gao JR, Hou LF, Jia JH, Han L, Ye Q, Li YJ. Tetrahedron 2013; 69: 9033
15b Li YJ, Huang HH, Ju J, Jia JH, Han L, Ye Q, Yu WB, Gao JR. RSC Adv. 2013; 3: 25840
15c Li YJ, Huang HM, Dong HQ, Jia JH, Han L, Ye Q, Gao JR. J. Org. Chem. 2013; 78: 9424

16 Huang HM, Gao JR, Ye Q, Yu WB, Sheng WJ, Li YJ. RSC Adv. 2014; 4: 15526
17 Galenko VV, Khlebnikov AF, Novikov MS, Avdontceva MS. Tetrahedron 2015; 71: 1940
18 All chemicals were purchased from commercial vendors and were used as received without further purification. The ¹H and ¹³C NMR spectra were recorded at 500 and 125 MHz, respectively, in CDCl₃ using TMS as internal standard with a Bruker AM 500 spectrometer. Chemical shifts (δ) are reported as parts per million (ppm) and the following abbreviations are used to identify the multiplicities: s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet, b=broad and all combinations thereof can be explained by their integral parts. HRMS data were obtained with a Thermo Scientific LTQ Orbitrap XL mass spectrometer and the GC-MS were recorded with an Agilent (GC431-MS210). Thin-layer chromatography was performed on pre-coated glass-backed plates and visualized with UV light at 254 nm. Flash column chromatography was performed on silica gel (see the Supporting Information). Synthesis of 3a; Typical Procedure A mixture of chalcone 1a (0.25 mmol, 0.0520 g), diethyl iminodiacetate 2a (0.5 mmol, 0.0945 g), Et₃N (0.25 mmol, 0.0253 g), and Cu(OAc)₂ (0.25 mmol, 0.0498 g) was dissolved in DMF (1.0 mL) in a thick-walled tube (10 mL). The mixture was stirred at 100 °C for 8 h under air atmosphere, and the progress of the reaction was monitored by TLC (PE/EtOAc = 2:1 (v/v)). Upon completion, the mixture was cooled to r.t. and poured into saturated aqueous NaCl (10.0 mL) and extracted with EtOAc (3 × 10.0 mL). The acquired organic phases were combined and dried over anhydrous Na₂SO₄. After removing the volatile solvent, the product 3a was obtained as a white solid in 90% yield by isolation with silica column chromatography (eluting solvent: petroleum ether/EtOAc = 2:1 (v/v)).

Supplementary Material

Supporting Information