Citation: Yu Sifan, Fu Xiang, Liu Gengxin, Qiu Huang, Hu Wenhao. Efficient and Facile Synthesis of Chiral Sulfonamides via Asymmetric Multicomponent Reactions[J]. Acta Chimica Sinica, ;2018, 76(11): 895-900. doi: 10.6023/A18060228 shu

Efficient and Facile Synthesis of Chiral Sulfonamides via Asymmetric Multicomponent Reactions

School of Pharmaceutical Sciences, Sun Yat-Sen University, Guangzhou 510006

Corresponding author: Qiu Huang, qiuhuang@mail.sysu.edu.cn Hu Wenhao, huwh9@mail.sysu.edu.cn
Received Date: 11 June 2018
Available Online: 24 November 2018
Fund Project: the Guangdong Innovative and Entrepreneurial Research Team Program 2016ZT06Y337Project supported by the Guangdong Innovative and Entrepreneurial Research Team Program (No. 2016ZT06Y337)

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Sulfonamide is a key structural unit of several groups of vitally synthetic drugs that have been extensively used as antimicrobials, antiretroviral drugs and anticancer agents. In particular, enantiomerically pure sulfonamides represent a rapidly-increasing important substance in new drug discovery due to their unique pharmacological properties. Thus, developing asymmetric synthetic methods involving rapid and highly efficient construction of these compounds is extremely important and highly demanded for medicinal chemists. In our laboratory, we have reported a serial of asymmetric multicomponent reactions via trapping reactive ammonium ylides generated from amines and diazo compounds in the presence of transition metal complexes and chiral phosphoric acids. In this work, an asymmetric three-component reaction of sulfonamides, diazo compounds and imines cooperatively catalyzed by Rh₂(OAc)₄ and chiral phosphoric acids was reported. This Rh₂(OAc)₄ and chiral phosphoric acids cooperatively catalyzed three-component reaction of sulfonamides, diazo compounds and imines accomplished with satisfying yields (up to 85%), high diastereoselectivity (>20:1) and excellent enantioselectivity (up to 99% ee), thus providing a rapid access to synthesize enantiomerically enriched sulfonamides bearing two adjacent chiral carbons. Furthermore, this newly developed three-component reaction was carried out on a gram-scale with a lower catalyst loading and without impacting the yield, diastereoselectivity and enantioselectivity. Finally, we explored the further transformation of obtained three-component reaction products:1) treatment of 5aaa with LiAlH₄ under 0℃ in THF for 8.0 h gave the corresponding alcohol derivative 6 in 82% yield without changing the diastereoselectivity and enantioselectivity (0.20 mmol scale); 2) treatment of 5aaa with triphosgene and triethylamine under 0℃ in DCM for 1.0 h, gave five-membered heterocyclic sulfoximine derivative 7 bearing three adjacent chiral atoms (2 carbons and 1 sulfur) in 80% yield with perfect diastereoselectivity (>20:1) and remained enantioselectivity (0.20 mmol scale).
- sulfonamides,
- asymmetric multicomponent reactions,
- ammonium ylides,
- cooperative catalysis,
- sulfoximines
1. [1]
  (a) McGrath, N. A.; Brichacek, M.; Njardarson, J. T. J. Chem. Educ. 2010, 87, 1348. (b) Dai, H.; Stepan, A. F.; Plummer, M. S.; Zhang, Y.; Yu, J. J. Am. Chem. Soc. 2011, 133, 7222. (c) Laha, J. K.; Dayal, N.; Jethava, K. P.; Prajapati, D. V. Org. Lett. 2015. 17, 1296. (d) Deng, Y.; Li, B.; Zhang, T. Environ. Sci. Technol. 2018, 52, 3854. (e) Ran, Y.; Yang, Y.; You, H.; You, J. ACS Catal. 2018, 8, 1796.
2. [2]
3. [3]
4. [4]
  (a) Rocheblave, L.; Bihel, F.; De Michelis, C.; Priem, G.; Courcambeck, J.; Bonnet, B.; Chermann, J. C.; Kraus, J. L. J. Med. Chem. 2002, 45, 3321. (b) Kovalevsky, A. Y.; Ghosh, A. K.; Weber, I. T. J. Med. Chem. 2008, 51, 6599. (c) Gerlits, O. O.; Keen, D. A.; Blakeley, M. P.; Louis, J. M.; Weber, I. T.; Kovalevsky, A. Y. J. Med. Chem. 2017, 60, 2018.
5. [5]
  (a) Blacklock, T. J.; Sohar, P.; Butcher, J. W.; Lamanec, T.; Grabowski, E. J. J. J. Org. Chem. 1993, 58, 1672. (b) Huang, Q.; Rui, E. Y.; Cobbs, M.; Dinh, D. M.; Gukasyan, H. J.; Lafontaine, J. A.; Mehta, S.; Patterson, B. D.; Rewolinski, D. A.; Richardson, P. F.; Edwards, M. P. J. Med. Chem. 2015, 58, 2821. (c) Pritzius, A. B.; Breit, B. Angew. Chem., Int. Ed, 2015, 54, 3121. (d) Fu, J.; Sun, F.; Liu, W.; Liu, W.; Gedam, M.; Hu, Q.; Fridley, C.; Quigley, H. A.; Hanes, J.; Pitha, I. Mol. Pharmaceutics. 2016, 13, 2987.
6. [6]
  (a) Poole, R. M. Drugs 2014, 74, 1559. (b) Scola, P. M.; Sun, L.; Wang, A. X.; Chen, J.; Sin, N.; Venables, B. L.; Sit, S.; Chen, Y.; Cocuzza, A.; Bilder, D.; Zhang, B.; Hewawasam, P.; Tu, Y.; Friborg, J.; Falk, P.; Hernandez, D.; Levine, S.; Chen, C.; Yu, F.; Zvyaga, T.; Good, A. C.; Rajamani, R.; Kish, K.; Tredup, J.; Klei, H. E.; Gao, Q.; Mueller, L.; Colonno, R. J.; Grasela, D. M.; Shi, H.; Sun, L.; Warner, W.; Li, D.; Zhu, J.; Meanwell, N. A.; McPhee, F. J. Med. Chem. 2014, 57, 1730. (c) Zheng, B.; D'Andrea, S. V.; Sun, L. ACS Med. Chem. Lett. 2018, DOI: 10.1021/acsmedchemlett.7b00503.
7. [7]
  (a) Combs, A. P.; Zhu, W.; Crawley, M. L.; Glass, B.; Polam, P.; Sparks, R. B.; Modi, D.; Takvorian, A.; McLaughlin, E.; Yue, E. W.; Wasserman, Z.; Bower, M.; Wei, M.; Rupar M.; Ala, P. J.; Reid, B. M.; Ellis, B.; Gonneville, L.; Emm, T.; Taylor, N.; Yeleswaram, S.; Li, Y.; Wynn, R.; Burn, T. C.; Hollis, G.; Liu, P. C. C.; Metcalf, B. J. Med. Chem. 2006, 49, 3774. (b) Liu, p.; Lanza, T. J.; Chioda, M.; Jones, C.; Chobanian, H. R.; Guo, Y.; Chang, L.; Kelly, T. M.; Kan, Y.; Wang, S.; Strack, A. M.; Miller, R.; Pang, J.; Lyons, K.; Dragovic, J.; Ning, J. G.; Schafer, W. A.; Welch, C. J.; Gong, X.; Gao, Y.; Hornak, V.; Ball, R. G.; Tsou, N.; Reitman, M. L.; Wyvratt, M. J.; Nargund, R. P.; Lin, L. S. ACS Med. Chem. Lett. 2011, 2, 933. (c) Maso, M. J. D.; Nepomuceno, G. M.; Peter, M. A. S.; Gitre, H. H.; Martin, K. S.; Shaw, J. T. Org. Lett. 2016, 18, 1740. (d) Rajkumar, S.; Clarkson, G. J.; Shipman, M. Org. Lett. 2017, 19, 2058. (e) Li, K.; Weber, A. E.; Tseng, L.; Malcolmson, S. J. Org. Lett. 2017, 19, 4239.
8. [8]
  (a) Zhong, F.; Wang, Y.; Han, X.; Huang, K.; Lu, Y. Org. Lett. 2011, 13, 1310. (b) Turnpenny, T. W.; Hyman, K. L.; Chemler, S. R. Organometallics 2012, 31, 7819. (c) Hou, W.; Wei, Q.; Liu, G.; Chen, J.; Guo, J.; Peng, Y. Org. Lett. 2015, 17, 4870. (d) Beisel, T.; Diehl, A. M.; Manolikakes, G. Org. Lett. 2016, 18, 4116. (e) Dydio, P.; Key, H. M.; Hayashi, H.; Clark, D. S.; Hartwig, J. F. J. Am. Chem. Soc. 2017, 139, 1750. (f) Mennie, K. M.; Banik, S. M.; Reichert, E. C.; Jacobsen, E. N. J. Am. Chem. Soc. 2018, 140, 4797.
9. [9]
  (a) Graaff, C. D.; Ruijter, E.; Orru, R. V. A. Chem. Soc. Rev. 2012, 41, 3969. (b) Grondal, C.; Jeanty, M.; Enders, D. Nat. Chem. 2010, 2, 167. (c) Zhang, D.; Hu, W. Chem. Rec. 2017, 17, 739.
10. [10]
11. [11]
12. [12]
  (a) Wang, Y.; Zhu, Y.; Chen, Z.; Mi, A.; Hu, W.; Doyle, M. P. Org. Lett. 2003, 5, 3923. (b) Wang, Y.; Chen, Z.; Mi, A.; Hu, W. Chem. Commun. 2004, 2486. (c) Jiang, J.; Xu, H.; Xi, J.; Ren, B.; Lv, F.; Guo, X.; Jiang, L.; Zhang, Z.; Hu, W. J. Am. Chem. Soc. 2011, 133, 8428. (d) Jiang, L.; Zhang, D.; Wang, Z.; Hu, W. Synthesis 2013, 45, 452. (e) Ren, L.; Lian, X.; Gong, L. Chem. Eur. J. 2013, 19, 3315. (f) Ma, X.; Jiang, J.; Lv, S.; Yao, W.; Yang, Y.; Liu, S.; Xia, F.; Hu, W. Angew. Chem., Int. Ed. 2014, 53, 13136. (g) Jiang, J.; Ma, X.; Liu, S.; Qian, Y.; Lv, F.; Qiu, L.; Wu, X.; Hu, W. Chem. Commun. 2013, 49, 4238. (h) Lei, R.; Wu, Y.; Dong, S.; Jia, K.; Liu, S.; Hu, W. J. Org. Chem. 2017, 82, 2862.
13. [13]
  http://ccc.chem.pitt.edu/wipf/MechOMs/evans_pKa_table.pdf
14. [14]
  Qiu, H.; Li, M.; Jiang, L.; Lv, F.; Zan, L.; Zhai, C.; Doyle, M.; Hu, W. Nat. Chem. 2012, 4, 733. doi: 10.1038/nchem.1406
15. [15]
16. [16]
  (a) Okamura, H.; Bolm, C. Org. Lett. 2004, 6, 1305. (b) Aithagani, S. K.; Dara, S.; Munagala, G.; Aruri, H.; Yadav, M.; Sharma, S.; Vishwakarma, R. A.; Singh, S. P. Org. Lett. 2015, 17, 5547.
17. [17]
  Dong, S.; Frings, M.; Cheng, H.; Wen, J.; Zhang, D.; Raabe, G.; Bolm, C. J. Am. Chem. Soc. 2016, 138, 2166. doi: 10.1021/jacs.6b00143
18. [18]
  Kang, Z.; Zhang, D.; Shou, J.; Hu, W. Org. Lett. 2018, 20, 983. doi: 10.1021/acs.orglett.7b03916
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