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)

Figures(5)

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
1. [1]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
2. [2]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
3. [3]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
4. [4]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
5. [5]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
6. [6]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
7. [7]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-. doi: 10.3866/PKU.WHXB202312010
8. [8]
  Linbao Zhang , Weisi Guo , Shuwen Wang , Ran Song , Ming Li . Electrochemical Oxidation of Sulfides to Sulfoxides. University Chemistry, 2024, 39(11): 204-209. doi: 10.3866/PKU.DXHX202401009
9. [9]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
10. [10]
  Daojuan Cheng , Fang Fang . Exploration and Implementation of Science-Education Integration in Organic Chemistry Teaching for Pharmacy Majors: A Case Study on Nucleophilic Substitution Reactions of Alkyl Halides. University Chemistry, 2024, 39(11): 72-78. doi: 10.12461/PKU.DXHX202403105
11. [11]
  Qianqian Liu , Xing Du , Wanfei Li , Wei-Lin Dai , Bo Liu . Synergistic Effects of Internal Electric and Dipole Fields in SnNb₂O₆/Nitrogen-Enriched C₃N₅ S-Scheme Heterojunction for Boosting Photocatalytic Performance. Acta Physico-Chimica Sinica, 2024, 40(10): 2311016-. doi: 10.3866/PKU.WHXB202311016
12. [12]
  Hao Wu , Zhen Liu , Dachang Bai . ¹H NMR Spectrum of Amide Compounds. University Chemistry, 2024, 39(3): 231-238. doi: 10.3866/PKU.DXHX202309020
13. [13]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
14. [14]
  Jingjie Tang , Luying Xie , Jiayu Liu , Shangyu Shi , Xinyu Sun , Jiayang Lin , Qikun Yang , Chuan'ang Yu , Zecheng Wang , Yingying Wang , Zengyang Xie . Efficient Rapid Synthesis and Antibacterial Activities of Tosylhydrazones: A Recommended Innovative Chemistry Experiment for Undergraduate Medical University. University Chemistry, 2024, 39(3): 316-326. doi: 10.3866/PKU.DXHX202309091
15. [15]
  Zhen Yao , Bing Lin , Youping Tian , Tao Li , Wenhui Zhang , Xiongwei Liu , Wude Yang . Visible-Light-Mediated One-Pot Synthesis of Secondary Amines and Mechanistic Exploration. University Chemistry, 2024, 39(5): 201-208. doi: 10.3866/PKU.DXHX202311033
16. [16]
  Meijin Li , Xirong Fu , Xue Zheng , Yuhan Liu , Bao Li . The Marvel of NAD⁺: Nicotinamide Adenine Dinucleotide. University Chemistry, 2024, 39(9): 35-39. doi: 10.12461/PKU.DXHX202401027
17. [17]
  Hong Zheng , Xin Peng , Chunwang Yi . The Tale of Caprolactam Cyclic Oligomers: The Ever-changing Life of “Princess Cyclo”. University Chemistry, 2024, 39(9): 40-47. doi: 10.12461/PKU.DXHX202403058
18. [18]
  Yuena Yu , Fang Fang . Microwave-Assisted Synthesis of Safinamide Methanesulfonate. University Chemistry, 2024, 39(11): 210-216. doi: 10.3866/PKU.DXHX202401076
19. [19]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
20. [20]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060

Get Citation

PDF

XML

Metrics

PDF Downloads(22)
Abstract views(1410)
HTML views(210)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142