Synthesis 2022; 54(05): 1329-1338
DOI: 10.1055/a-1672-5707
paper

Enantioselective Construction of Multi-Nitrogen-Containing Spirocycles: Asymmetric [3+2] Annulation of 4-Isothiocyanato­pyrazolones with Azodicarboxylates

Shiqiang Wei
,
Wenyao Wang
,
Aiqi Xue
,
,
Jingping Qu
,
Baomin Wang
We thank the Fundamental Research Funds for the Central Universities (No. DUT21LAB134) for support of this work.


Abstract

The 4-isothiocyanatopyrazolones were exploited as a class of efficient synthons for the construction of triazoline derivatives via asymmetric [3+2] annulation with azodicarboxylates, providing a wide range of structurally diverse multi-nitrogen-containing spirocycles in excellent yields (up to 97%) with excellent enantioselectivities (up to 97% ee).

Supporting Information



Publication History

Received: 11 August 2021

Accepted after revision: 19 October 2021

Accepted Manuscript online:
19 October 2021

Article published online:
29 November 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References

    • 1a Pathak T. Chem. Rev. 2002; 102: 1623
    • 1b O’Connor SE, Maresh JJ. Nat. Prod. Rep. 2006; 23: 532
    • 1c de Sá Alves FR, Barreiro EJ, Fraga CA. M. Mini-Rev. Med. Chem. 2009; 9: 782
    • 1d Barve IJ, Dalvi PB, Thikekar TU, Chanda K, Liu Y.-L, Fang C.-P, Liu C.-C, Sun C.-M. RSC Adv. 2015; 5: 73169
    • 2a Ferreira LG, Dos Santos RN, Oliva G, Andricopulo AD. Molecules 2015; 20: 13384
    • 2b Chen Q.-H, Yu K, Zhang X, Chen G, Hoover A, Leon F, Wang R, Subrahmanyam N, Mekuria EA, Rakotondraibe LH. Bioorg. Med. Chem. Lett. 2015; 25: 4553
    • 2c Velthuisen EJ, Johns BA, Temelkoff DP, Brown KW, Danehower SC. Eur. J. Med. Chem. 2016; 117: 99
    • 2d Ortega JA, Arencibia JM, Sala GL, Borgogno M, Bauer I, Bono L, Braccia C, Armirotti A, Girotto S, Ganesan M, Vivo D. J. Med. Chem. 2017; 60: 5800
    • 2e Che J, Wang Z, Sheng H, Huang F, Dong X, Hu Y, Xie X, Hu Y. R. Soc. Open Sci. 2018; 5: 180176
    • 3a Todoulou OG, Papadaki-Valiraki AE, Ikeda SC, De Clercq E. Eur. J. Med. Chem. 1994; 29: 611
    • 3b Morphy R, Kay C, Rankovic Z. Drug Discov. Today 2004; 9: 641
    • 3c Bekircan O, Kahveci B, Küçük M. Turk. J. Chem. 2006; 30: 29
    • 3d Zhang Q, Peng YY, Wang XI, Keenan SM, Arora S, Welsh WJ. J. Med. Chem. 2007; 50: 749
    • 3e Valentina P, Ilango K, Kathiravan MK. Arch. Pharm. Res. 2016; 39: 1382
    • 3f Huggins WM, Minrovic BM, Corey BW, Jacobs AC, Melander RJ, Sommer RD, Zurawski DV, Melander C. ACS Med. Chem. Lett. 2017; 8: 27
    • 4a Brogden RN. Drugs 1986; 32: 60
    • 4b Kakiuchi Y, Sasaki N, Satoh-Masuoka M, Murofushi H, Murakami-Murofushi K. Biochem. Biophys. Res. Commun. 2004; 320: 1351
    • 4c Chande MS, Barve PA, Suryanarayan V. J. Heterocycl. Chem. 2007; 44: 49
    • 4d Varvounis G. Adv. Heterocycl. Chem. 2009; 98: 143
    • 4e Schlemminger I, Schmidt B, Flockerzi D, Tenor H, Zitt C, Hatzelmann A, Marx D, Braun C, Külzer R, Heuser A, Kley HP, Sterk GJ. WO 2010055083, 2010
    • 4f Schmidt A, Dreger A. Curr. Org. Chem. 2011; 15: 1423
    • 4g Fustero S, Sánchez-Roselló M, Barrio P, Simón-Fuentes A. Chem. Rev. 2011; 111: 6984
    • 4h Kumar V, Kaur K, Gupta GK, Sharma AK. Eur. J. Med. Chem. 2013; 69: 735
    • 4i Felix W, Edgar S, Martin N, Marc N, Anja B, Andreas L. Mol. Diversity 2014; 18: 483
    • 4j Silaychev PS, Filimonov VO, Maslivets AN, Makhmudov RR. RU 2577528, 2014

      For selected examples, see:
    • 5a Kolasa T, Miller M. Tetrahedron Lett. 1988; 29: 4661
    • 5b Ibata T, Isogami Y, Tamura H. Chem. Lett. 1988; 1551
    • 5c Hassner A, Fischer B. Tetrahedron 1989; 45: 3535
    • 5d Andersonand DJ, Watt W. J. Heterocycl. Chem. 1995; 32: 1525
    • 5e Tsuge O, Hatta T, Tashiro H, Maeda H. Heterocycles 2001; 55: 243
    • 5f Saleem RS. Z, Tepe JJ. J. Org. Chem. 2010; 75: 4330
    • 6a Chauhan P, Mahajan S, Enders D. Chem. Commun. 2015; 51: 12890
    • 6b Liu S, Bao X, Wang B. Chem. Commun. 2018; 54: 11515
    • 7a Monge D, Jensen KL, Marín R, Jørgensen KA. Org. Lett. 2011; 13: 328
    • 7b Wang M, Liu X, He P, Lin L, Feng X. Chem. Commun. 2013; 49: 2572
    • 7c Shao Q, Chen J, Tu M, Piotrowski DW, Huang Y. Chem. Commun. 2013; 49: 11098
    • 7d Zhao M.-X, Bi H.-L, Zhou H, Yang H, Shi M. J. Org. Chem. 2013; 78: 9377
    • 7e Jiang Y, Pei C.-K, Du D, Li X.-G, He Y.-N, Xu Q, Shi M. Eur. J. Org. Chem. 2013; 7895
    • 7f Ma B, Luo W, Lin L, Liu X, Feng X. Chem. Commun. 2017; 53: 4077
    • 7g Zhang L.-J, Zhang S.-X, Fu L.-N, Li X.-Y, Guo Q.-X. RSC Adv. 2017; 7: 18714

      For selected examples of spiroprazolones, see:
    • 8a Yetra SR, Mondal S, Mukherjee S, Gonnade RG, Biju AT. Angew. Chem. Int. Ed. 2016; 55: 268
    • 8b Hack D, Dürr AB, Deckers K, Chauhan P, Seling N, Rübenach L, Mertens L, Raabe G, Schoenebeck F, Enders D. Angew. Chem. Int. Ed. 2016; 55: 1797
    • 8c Yang W, Sun W, Zhang C, Wang Q, Guo Z, Mao B, Liao J, Guo H. ACS Catal. 2017; 7: 3142
    • 8d Wang S, Izquierdo J, Rodríguez-Escrich C, Pericàs MA. ACS Catal. 2017; 7: 2780
    • 8e Liu J.-Y, Zhao J, Zhang J.-L, Xu P.-F. Org. Lett. 2017; 19: 1846
    • 8f Zheng J, Wang S.-B, Zheng C, You S.-L. Angew. Chem. Int. Ed. 2017; 56: 4540
    • 9a Meninno S, Roselli A, Capobianco A, Overgaard J, Lattanzi A. Org. Lett. 2017; 19: 5030
    • 9b Kaya U, Chauhan P, Mahajan S, Deckers K, Valkonen A, Rissanen K, Enders D. Angew. Chem. Int. Ed. 2017; 56: 1
    • 9c Zhou J, Huang W.-J, Jiang G.-F. Org. Lett. 2018; 20: 1158
    • 9d Chu M.-M, Qi S.-S, Wang Y.-F, Wang B, Jiang Z.-H, Xu D.-Q, Xu Z.-Y. Org. Chem. Front. 2019; 6: 1977
    • 9e Šimek M, Remeš M, Veselý J, Rios R. Asian J. Org. Chem. 2013; 2: 64
    • 9f Šeferna FV, Meazza M, Rios R, Patil M, Veselýur J. Eur. J. Org. Chem. 2021; 1
    • 10a Bao X, Wei S, Qian X, Qu J, Wang B, Zou L, Ge G. Org. Lett. 2018; 20: 3394
    • 10b Wei S, Bao X, Wang W, Nawaz S, Dai Q, Qu J, Wang B. Chem. Commun. 2020; 56: 10690
    • 10c Wang W, Bao X, Wei S, Nawaz S, Qu J, Wang B. Chem. Commun. 2021; 57: 363
    • 11a Brackmann F, Meijere de A. Chem. Rev. 2007; 107: 4538
    • 11b Gagnon A, Duplessis M, Fader L. Org. Prep. Proced. Int. 2010; 42: 1
    • 11c Pellissier H. Tetrahedron 2014; 70: 4991