苯亚磺酸钠和叔胺电化学耦合生成β-氨基乙烯砜

doi:10.6023/cjoc202012051

摘要/Abstract

β-氨基砜是一种特别有用的生物活性分子的骨架.β-氨基乙烯基砜加氢法是合成β-氨基砜的一种简便、高效的方法. 提出了一种以苯亚磺酸钠和叔胺为底物的电化学法合成β-氨基乙烯基砜. 在无金属催化剂和无氧化剂的条件下, 仅合成E构型的β-氨基乙烯基砜. 循环伏安实验和对照实验表明, 该电合成反应经历了磺酸自由基与烯胺的加成, 并生成碳自由基的过程.

关键词: β-氨基砜, β-氨基乙烯基砜, 苯亚磺酸钠, 叔胺

β-Amido sulfone motif reprents a particularly useful scaffold for the biologically active molecules. The hydrogenation ofβ-amidovinyl sulfon is an alternative method to synthesizeβ-amido sulfone. Herein, one electrochemical method to synthesizeβ-amido sulfone using sodium sulfites and tertiary amines as substrates is presented. OnlyE-configurations ofβ-amidovinyl sulfonyl were synthesized under metal catalyst- and oxidant-free condition. Cyclic voltammetry (CV) and control experiments indicate that this electrosynthesis reaction goes through a radical process which the sulfonyl radical adds to enamine to form the carbon radical.

Key words: β-amido sulfone, β-amidovinyl sulfon, sodium sulfites, tertiary amines

引用此文

熊云奎, 张健叶, 申裙, 黄嘉宇, 王涛. 苯亚磺酸钠和叔胺电化学耦合生成β-氨基乙烯砜[J]. 有机化学, 2021, 41(7): 2735-2742.

Yunkui Xiong, Jianye Zhang, Qun Shen, Jiayu Huang, Tao Wang. Electrochemical Coupling of the Sulfonic Acid Sodium and Tertiary Amines for the Synthesis ofβ-Amidovinyl Sulfones[J]. Chinese Journal of Organic Chemistry, 2021, 41(7): 2735-2742.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 9

Figure 1. Example for biologically active sulfones

Figure 2. Examples for biologically active β-amido sulfones

Scheme 1. Some methodes for synthesizing β-amidovinyl sulfone

Entry	Variation form standard condition	yieldb/%
1	None	92 (83^c)
2	ⁿBu₄NBF₄ instead ofⁿBu₄NOAc	80
3	NaI instead ofⁿBu₄NOAc	80
4	THF/MeOH (V/V=9 mL/1 mL) as solvent	88
5	CH₃CN/AcOH (V/V=9 mL/0.5 mL) as solvent	N.d.^d
6	THF/H₂O (V/V=9 mL/1 mL) as solvent	47
7	CH₃CN (10 mL) as solvent	85
8	Air instead of N₂	42
9	Pt(+)\|Pt(–) instead of C(+)\|Pt(–)	60
10	Ni(+)\|Pt(–) instead of C(+)\|Pt(–)	35
11	Fe(+)\|Pt(–) instead of C(+)\|Pt(–)	Trace
12	without electric current	N.d.^d

Table 1. Optimization of the reaction conditionsa

Table 2. Substrate scope of β-amidovinyl sulfones from the sulfonic acid sodium derivatives and some tertiary aminesa

Scheme 2. Scale-up reaction

Figure 3. Cyclic voltammograms of 1a and 2a

Scheme 3. Control experiments

Scheme 4. Proposed mechanism

参考文献 27

[1]	(a) Tucker, H.; Crook,J. W.; Chesterson,G. J. J. Med. Chem. 1988, 31,954. doi: 10.1021/jm00400a011
	(b) Couderchet, M.; Schmalfu, J.; Böger, P. Pestic. Sci. 1998, 52,381. doi: 10.1002/(SICI)1096-9063(199804)52:4【-逻辑与-】#x00026;lt;【-逻辑与-】#x00026;gt;1.0.CO;2-7
	(c)Busch-Petersen JakobUS 2007/249672, 2007.
	(d) Grove,J. -D.C.; Abingdon,S. J.D.; Abingdon,R. K., US 2013/ 115310. 2013.
	(e) Duan, J.; Dhar,T. G.M., WO 2015/103510, 2015.
[2]	Goadsby,P. J.; Ferrari,M. D.; Olesen, J.; Stovner,L. J.; Senard, M.; Jackson,N. C.; Poole,P. H. Neurology 2000, 4,156.
[3]	Wozel,G. C.; Blasum, C. Arch. Dermatol. Res. 2014, 306,103. doi: 10.1007/s00403-013-1409-7
[4]	Iversen, P.; Tyrrell, C.J; Kaisary,A. V.; Anderson, J.B; van Poppel, H.; Tammela,T. L.J.; Chamberlain, M.; Carroll, K.; Melezinek, I. J. Urol. 2000, 164,1579. doi: 10.1016/S0022-5347(05)67032-2
[5]	For some selected examples, see: (a) Xia, H.; An, Y.; Zeng, X.; Wu,, J. Chem. Commun. 2017, 53,12548. doi: 10.1039/C7CC07279A
	(b) Wang, K.; Wang, G.; Duana, G; Xia, C. RSC Adv. 2017, 7,51313. doi: 10.1039/C7RA11363C
	(c) Xia, H.; An, Y; Zeng, X.; Wu, J. Org. Chem. Front. 2018, 5,366. doi: 10.1039/C7QO00866J
	(d) Karmakar, U.; Samanta, R. J. Org. Chem. 2019, 84,2850. doi: 10.1021/acs.joc.8b03098
	(e) Griffiths,R. J.; Kong,W. C.; Richards,S. A.; Burley,G. A.; Willis,M. C.; Talbot,E. P.A. Chem. Sci. 2018, 9,2295. doi: 10.1039/C7SC04900E
	(f) Du, B.; Qian, P.; Wang, Y.; Mei, H.; Han, J.; Pan, Y. Org. Lett. 2016, 18,4144. doi: 10.1021/acs.orglett.6b02289
	(g) Liang, S.; Manolikakes, G. Adv. Synth. Catal. 2016, 358,2371. doi: 10.1002/adsc.201600388
	(h) Rao,W. H.; Shi,B. F. Org. Lett. 2015, 17,2784. doi: 10.1021/acs.orglett.5b01198
	(i) Liu, J.; Yu, L.; Zhuang, S.; Gui, Q.; Chen, X.; Wang, W.; Tan, Z. Chem. Commun. 2015, 51,6418. doi: 10.1039/C5CC00202H
	(j) Xu, Y.; Liu, P.; Li,S. L.; Sun, P. J. Org. Chem. 2015, 80,1269. doi: 10.1021/jo5026095
	(k) Wu, Z.; Song, H.; Cui, X.; Pi, C.; Du, W.; Wu, Y. Org. Lett. 2013, 15,1270. doi: 10.1021/ol400178k
	(l) Saidi, O.; Marafie, J.; Ledger,A. E.W.; Liu,P. M.; Mahon,M. F.; Kociok-Köhn, G.; Whittlesey,M. K.; Frost,C. G. J. Am. Chem. Soc. 2011, 133,19298. doi: 10.1021/ja208286b
	(m) Zhao, X.; Dimitrijevic, E.; Dong,V. M. J. Am. Chem. Soc. 2009, 131,3466. doi: 10.1021/ja900200g
[6]	Wang, Q.; Sasaki,N. A.; Riche, C.; Potier, P. Tetrahedron 2001, 57,6455. doi: 10.1016/S0040-4020(01)00537-3
[7]	Carretero,J. C.; Arrayas, R.G; Gracia,I. S. Tetrahedron Lett. 1997, 38,8537. doi: 10.1016/S0040-4039(97)10241-6
[8]	Monn,J. A.; Massey,S. M.; Valli,M. J.; Henry,S. S.; Stephenson,G. A.; Bures, M.; Hérin, M.; Catlow, J.; Giera, D.; Wright,R. A.; Johnson,B. G.; Andis,S. L.; Kingston, A.; Schoepp,D. D. J. Med. Chem. 2007, 50,233. doi: 10.1021/jm060917u
[9]	Man,H. W.; Schafer, P.; Wong,L. M.; Patterson,R. T.; Corral,L. G.; Raymon, H.; Blease, K.; Leisten, J.; Shirley,M. A.; Tang, Y.; Babusis,D. M.; Chen, R.; Stirling, D.; Muller,G. W. J. Med. Chem. 2009, 52,1522. doi: 10.1021/jm900210d
[10]	Shariati, A.; Dadashi, M.; Chegini, Z.; Belkum, A.; Mirzaii, M.; Khoramrooz,S. S.; Davood,D. S. Antimicrob. Resist. Infect. Control 2020, 9,56. doi: 10.1186/s13756-020-00714-9
[11]	Ermolenko, L.; Sasaki,N. A.; Potier, P. J. Chem. Soc., erkin Trans. 1 2000,2465.
[12]	Kramer, P.; Krieg,S. C.; Kelm, H.; Manolikakes, G. Org. Biomol. Chem. 2019, 17,5538. doi: 10.1039/C9OB00825J
[13]	Lin,Y. S.; Ali,B. E.; Alper, H. J. Am. Chem. Soc. 2001, 123,7719. doi: 10.1021/ja010923+
[14]	Xu,Y. H.; Wang, M.; Lu, P.; Loh,T. P. Tetrahedron 2013, 69,4403. doi: 10.1016/j.tet.2013.01.071
[15]	Jiang, H.; Chen, X.; Zhang, Y.; Yu, S. Adv. Synth. Catal. 2013, 355,809. doi: 10.1002/adsc.201200874
[16]	Sun,D. L.; Zhang,R. H. Org. Chem. Front. 2018, 5,92. doi: 10.1039/C7QO00729A
[17]	Zhu,T. H.; Zhang,X. C.; Zhao, K.; Loh,T. P. Org. Chem. Front. 2019, 6,94. doi: 10.1039/C8QO01144C
[18]	(a) Cai, Y.; Zhang, R.; Sun, D.; Xu, S.; Zhou, Q. Synlett 2017, 28,1630. doi: 10.1055/s-0036-1588828
	(b) Chen, M.; Huang,Z. T.; Zheng,Q. Y. Org. Biomol. Chem. 2014, 12,9337. doi: 10.1039/C4OB01713G
[19]	Zhang,H. Y.; Tang,R. P.; Shi,X. L.; Xie L.; Wu,J. W. Chin. J. Org. Chem. 2019, 39,1837 (in Chinese). doi: 10.6023/cjoc201902006
	( 张怀远, 唐蓉萍, 石星丽, 颉林, 伍家卫, 有机化学, 2019, 39,1837.)
[20]	Feng,E. Q.; Hou,Z. W.; Xu,H. C. Chin. J. Org. Chem. 2019, 39,1424 (in Chinese). doi: 10.6023/cjoc201812007
	( 冯恩祺, 侯中伟, 徐海超, 有机化学, 2019, 39,1424.)
[21]	Pan, C.; Liu, P.; Wu,A. G.; Li, M.; Wen,L. R.; Guo,W. S. J. Org. Chem. 2020, 40,2855.
[22]	Zeng, L.; Li, H.; Hu, J.; Zhang, D.; Hu, J.; Peng, P.; Wang, S.; Shi, R.; Peng, J.; Pao,C. W.; Chen,J. L.; Lee,J. F.; Zhang, H.; Chen,Y. H.; Lei,A. W. Nat. Catal. 2020, 3,438. doi: 10.1038/s41929-020-0443-z
[23]	Sheng, J.; Wu, N.; Liu, X.; Liu, F.; Liu, S.; Ding,W. J.; Liu, C.; Cheng, X. J. Org. Chem. 2020, 40,3873.
[24]	Nu, C.; Wang,G. W. Chin. J. Org. Chem. 2020, 40,3633 (in Chinese). doi: 10.6023/cjoc202006081
	( 牛闯, 王官武, 有机化学, 2020, 40,3633.)
[25]	Jiang,M. B.; Yuan, Y.; Wang, T.; Xiong,Y. K.; Li, J.; Guo,H. J.; Lei,A. W. Chem. Commun. 2019,13852.
[26]	Sheykan, M.; Khani, S.; Abbasnia, M.; Shaabanzadeh, S.; Joafshan, M. Green Chem. 2017, 19,5940. doi: 10.1039/C7GC03141F
[27]	Kim,H. S.; Lee, S. Eur. J. Org. Chem. 2019,6951.