Diastereoselective Synthesis of Spiropyrazolones via 1,3-Dipolar [3+2] Cycloadditions between Pyrazolone-Based Olefins and N,N′-Cyclic Azomethine Imines

Abstract

Under the catalysis of PhCO₂H, the 1,3-dipolar [3+2] cyclo­addition between pyrazolone-based olefins and N,N′-cyclic azomethine imines proceeded readily, thus delivering structurally novel spiropyrazolones with up to 98% yield and >20:1 dr. The relative stereochemical configuration of the obtained spiropyrazolones was unambiguously ­assigned by X-ray single-crystal structure analysis. The diastereoselective formation of the title spiropyrazolones was interpreted by the hypothesized reaction mechanism.

Key words

1,3-dipolar [3+2] cycloaddition - pyrazolone-based olefin - N,N′-cyclic azomethine imine - spiropyrazolone - diastereoselectivity

Publication History

Received: 16 April 2021

Accepted after revision: 11 May 2021

Accepted Manuscript online:
11 May 2021

Article published online:
15 June 2021

• References and Notes


For selected examples, see:
• 1a Wu S, Li Y, Xu G, Chen S, Zhang Y, Liu N, Dong G, Miao C, Su H, Zhang W, Sheng C. Eur. J. Med. Chem. 2016; 115: 141
• 1b Zhang Y, Wu S, Wang S, Fang K, Dong G, Liu N, Miao Z, Yao J, Li J, Zhang W, Sheng C, Wang W. Eur. J. Org. Chem. 2015; 2030
• 1c Wang L, Yang Z, Ni T, Shi W, Guo Y, Li K, Shi A, Wu S, Sheng C. Bioorg. Med. Chem. Lett. 2020; 30: 126662
• 1d Chande MS, Barve PA, Suryanarayan V. J. Heterocycl. Chem. 2007; 44: 49
• 1e Han B, Xu S, Wang P. CN 104610148, 2015
• 1f Silaychev PS, Filimonov VO, Maslivets AN, Makhmudov RR. RU 2577528, 2014
• 1g Bao X, Wei S, Qian X, Qu J, Wang B, Zou L, Ge G. Org. Lett. 2018; 20: 3394

For a review, see:
• 2a Xie X, Xiang L, Peng C, Han B. Chem. Rec. 2019; 19: 2209

For selected examples, see:
• 2b Awasthi A, Yadav P, Kumar V, Tiwari DK. Adv. Synth. Catal. 2020; 362: 4378
• 2c Zhang J, Chan W.-L, Chen L, Ullah N, Lu Y. Org. Chem. Front. 2019; 6: 2210
• 2d Cheng C, Sun X, Miao Z. Org. Biomol. Chem. 2020; 18: 5577
• 2e Lin Y, Zhao B.-L, Du D.-M. J. Org. Chem. 2019; 84: 10209
• 2f Chen N, Zhu L, Gan L, Liu Z, Wang R, Cai X, Jiang X. Eur. J. Org. Chem. 2018; 2939
• 2g Maity R, Sahoo SC, Pan SC. Eur. J. Org. Chem. 2019; 2297
• 2h Wang C, Wen D, Chen H, Deng Y, Liu X, Liu X, Wang L, Gao F, Guo Y, Sun M, Wang K, Yan W. Org. Biomol. Chem. 2019; 17: 5514

For selected examples, see:
• 3a Mao B, Liu H, Yan Z, Xu Y, Xu J, Wang W, Wu Y, Guo H. Angew. Chem. Int. Ed. 2020; 59: 11316
• 3b da Silva AF, Leonarczyk IA, Ferreira MA. B, Jurberg ID. Org. Chem. Front. 2020; 7: 3599
• 3c Meninno S, Mazzanti A, Lattanzi A. Adv. Synth. Catal. 2019; 361: 79
• 3d Zhang Y, Wang C, Huang W, Haruehanroengra P, Peng C, Sheng J, Han B, He G. Org. Chem. Front. 2018; 5: 2229
• 3e Zhao C, Shi K, He G, Gu Q, Ru Z, Yang L, Zhong G. Org. Lett. 2019; 21: 7943
• 3f Mondal B, Maity R, Pan SC. J. Org. Chem. 2018; 83: 8645
• 3g Liang J.-Y, Shen S.-J, Chai X.-Q, Lv T. J. Org. Chem. 2018; 83: 12744
• 3h Luo W, Shao B, Li J, Xiao X, Song D, Ling F, Zhong W. Org. Chem. Front. 2020; 7: 1016

For selected examples, see:
• 4a Li H, Gontla R, Flegel J, Merten C, Ziegler S, Antonchick AP, Waldmann H. Angew. Chem. Int. Ed. 2019; 58: 307
• 4b Leng H.-J, Li Q.-Z, Zeng R, Dai Q.-S, Zhu H.-P, Liu Y, Huang W, Han B, Li J.-L. Adv. Synth. Catal. 2018; 360: 229
• 4c Xu J, Hu L, Hu H, Ge S, Liu X, Feng X. Org. Lett. 2019; 21: 1632
• 4d Sun B.-B, Chen J.-B, Zhang J.-Q, Yang X.-P, Lv H.-P, Wang Z, Wang X.-W. Org. Chem. Front. 2020; 7: 796
• 4e Sun B.-B, Zhang J.-Q, Chen J.-B, Fan W.-T, Yu J.-Q, Hu J.-M, Wang X.-W. Org. Chem. Front. 2019; 6: 1842
• 4f Ji Y.-L, Li H.-P, Ai Y.-Y, Li G, He X.-H, Huang W, Huang R.-Z, Han B. Org. Biomol. Chem. 2019; 17: 9217
• 4g Krishna AV, Reddy GS, Gorachand B, Ramachary DB. Eur. J. Org. Chem. 2020; 6623

For examples, see:
• 5a Li X, Chen F.-Y, Kang J.-W, Zhou J, Peng C, Huang W, Zhou M.-K, He G, Han B. J. Org. Chem. 2019; 84: 9138
• 5b Khairnar PV, Wu C.-Y, Lin Y.-F, Edukondalu A, Chen Y.-R, Lin W. Org. Lett. 2020; 22: 4760

For selected examples, see:
• 6a Cheng C, Zhang J, Wang X, Miao Z. J. Org. Chem. 2018; 83: 5450
• 6b Du J, Wu J.-H, Zhu L, Ren X, Jiang C, Wang T. Adv. Synth. Catal. 2020; 362: 2510
• 6c Cheng C, Sun X, Wu Z, Liu Q, Xiong L, Miao Z. Org. Biomol. Chem. 2019; 17: 3232
• 6d Shi Q, Zhang W, Wang Y, Qu L, Wei D. Org. Biomol. Chem. 2018; 16: 2301
• 6e Xu J, Yang W, Shi W, Mao B, Lin Y, Xiao Y, Guo H. Tetrahedron 2019; 75: 3609
• 6f Mutyala R, Reddy VR, Donthi R, Kallaganti VS. R, Chandra R. Tetrahedron Lett. 2019; 60: 703
• 6g Wang D, Wang X, Zhang XG, Miao ZW. Synthesis 2019; 51: 2149
• 6h Tan F, Su S, Liu Z. J. Heterocycl. Chem. 2020; 57: 2904

For a review, see:
• 7a Požgan F, Al Mamari H, Grošelj U, Svete J, Štefane B. Molecules 2018; 23: 3

For selected examples, see:
• 7b Xu X, Qian Y, Zavalij PY, Doyle MP. J. Am. Chem. Soc. 2013; 135: 1244
• 7c Gong J, Wan Q, Kang Q. Org. Lett. 2018; 20: 3354
• 7d Tong TM. T, Soeta T, Suga T, Kawamoto K, Hayashi Y, Ukaji Y. J. Org. Chem. 2017; 82: 1969
• 7e Volpe C, Meninno S, Capobianco A, Vigliotta G, Lattanzi A. Adv. Synth. Catal. 2019; 361: 1018
• 7f Fang Q.-Y, Jin H.-S, Wang R.-B, Zhao L.-M. Chem. Commun. 2019; 55: 10587
• 7g Li C, Wang C.-S, Li T.-Z, Mei G.-J, Shi F. Org. Lett. 2019; 21: 598
• 7h Yang Q.-Q, Yin X, He X.-L, Du W, Chen Y.-C. ACS Catal. 2019; 9: 1258
• 8 Typical Procedure and Characterization Data for 3aa A mixture of pyrazolone-based olefin 1a (1.0 equiv, 0.1 mmol), N,N′-cyclic azomethine imine 2a (1.25 equiv, 0.125 mmol), and PhCO₂H (20.0 mol%) in toluene (1.0 mL) was stirred at 110 ℃. After the reaction was completed as indicated by TLC plate, the solvent was removed by evaporation and the resulted crude product was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate, 4:1 to 2:1) to afford product trans-3aa (92% yield). Compound 3aa: white solid, yield 40.1 mg, 92%; mp 157.2–157.4 ℃. ¹H NMR (400 MHz, CDCl₃): δ = 7.82 (d, J = 7.6 Hz, 2 H), 7.44 (t, J = 8.0 Hz, 2 H), 7.33–7.24 (m, 9 H), 7.17 (d, J = 7.2 Hz, 2 H), 5.78 (s, 1 H), 4.43 (s, 1 H), 3.97–3.91 (m, 1 H), 3.28–3.21 (m, 1 H), 3.11–3.03 (m, 1 H), 3.00–2.91 (m, 1 H), 1.53 (s, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 173.6, 170.9, 159.5, 137.4, 135.4, 131.9, 129.1, 129.0, 128.94, 128.90, 128.2, 126.1, 125.7, 125.1, 119.3, 77.5, 72.9, 63.9, 47.9, 32.0, 17.2 ppm. HRMS (ESI): m/z calcd for C₂₇H₂₅N₄O₂ [M + H]⁺: 437.1972; found: 437.1964.
• 9 CCDC 2065581 (trans-3ak) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/structures.