Electrochemical Synthesis of Aryl Sulfonates from Sodium Sulfinates and Phenols under Metal-Free Conditions

doi:10.6023/cjoc202107060

Abstract

An electrochemical oxidative sulfonylation of phenols with sodium sulfinates has been established to produce arylsulfonyl esters with good functional group tolerance in moderate to high yields. The synthesis of chlorfenson and a gram-scale reaction have been performed to evaluate the practicality of this green protocol. Cyclic voltammetry experiments indicate that the oxidation of sulfinate occurs prior to that of phenol substrate under standard conditions, and free radical is involved in the process.

Key words: electrochemical synthesis, aryl sulfonates, metal-free conditions, green method

Cite this article

Zhengjiang Fu, Zhenjiang Yang, Li Sun, Jian Yin, Xuezheng Yi, Hu Cai, Aiwen Lei. Electrochemical Synthesis of Aryl Sulfonates from Sodium Sulfinates and Phenols under Metal-Free Conditions[J]. Chinese Journal of Organic Chemistry, 2022, 42(2): 600-606.

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Fig. & Tab. 8

Entry	Variation from the standard conditions	Yield^b/%
1	None	95 (90)^c
2	No water	25
3	No 15-crown-5	39
4	CH₃CN instead of DMF	49
5	13 mA instead of 11 mA	76
6	10 mA and 3.3 h instead of 11 mA and 3 h	85
7	Pt(+) instead of C(+)	82
8	Ni(–) instead of Pt(–)	60
9	No electricity	0

Table 1. Optimization of the reaction conditionsa

Table 2. Substrate scope of phenols with isolated yieldsa

Table 3. Substrate scope of phenols with isolated yieldsa

Scheme 1. Electrochemical oxidative sulfonylation of alcohols

Scheme 2. Synthesis of chlorfenson (3gf) and gram scale synthesis of phenyl benzenesulfonate (3aa)

Figure 1. Cyclic voltammograms of substrate 1a, 2a

Scheme 3. Radical-trapping experiment

Scheme 4. Proposed mechanism

References 20

[1]	(a) Stang, P. J.; Treptow, W. L. J. Med. Chem. 1981, 24, 468. pmid: 6267282
	(b) Yan, L.; Muller, C. E. J. Med. Chem. 2004, 47, 1031. doi: 10.1021/jm0310030 pmid: 6267282
	(c) Wang, P.; Min, J.; Nwachukwu, J. C.; Cavett, V.; Carlson, K. E.; Guo, P.; Zhu, M.; Zheng, Y.; Dong, C.; Katzenellenbogen, J. A.; Nettles, K. W.; Zhou, H. B. J. Med. Chem. 2012, 55, 2324. doi: 10.1021/jm201556r pmid: 6267282
	(d) Pisani, L.; Barletta, M.; Soto-Otero, R.; Nicolotti, O.; Mendez-Alvarez, E.; Catto, M.; Introcaso, A.; Stefanachi, A.; Cellamare, S.; Altomare, C.; Carotti, A. J. Med. Chem. 2013, 56, 2651. doi: 10.1021/jm4000769 pmid: 6267282
	(e) Ilardi, E. A.; Vitaku, E.; Njardarson, J. T. J. Med. Chem. 2014, 57, 2832. doi: 10.1021/jm401375q pmid: 6267282
	(f) Zheng, D.; Ma, H.; Ding, K. Chin. J. Org. Chem. 2017, 37, 1582. (in Chinese) doi: 10.6023/cjoc201701035 pmid: 6267282
	( 郑东青, 马海燕, 丁凯, 有机化学, 2017, 37, 1582.) doi: 10.6023/cjoc201701035 pmid: 6267282
	(g) Liu, A.; Liu, J.; Mei, H.; Röschenthaler, G.-V.; Han, J. Chin. J. Org. Chem. 2020, 40, 1926. (in Chinese) doi: 10.6023/cjoc202003004 pmid: 6267282
	( 刘爱遥, 刘江, 梅海波, Gerd-Volker, Röschenthalerc, 韩建林, 有机化学, 2020, 40, 1926.) doi: 10.6023/cjoc202003004 pmid: 6267282
[2]	(a) Mondal, S. Chem. Rev. 2012, 112, 5339. doi: 10.1021/cr2003294 pmid: 32486635
	(b) Rasheed, O. K.; Hardcastle, I. R.; Raftery, J.; Quayle, P. Org. Biomol. Chem. 2015, 13, 8048. doi: 10.1039/c5ob01239b pmid: 32486635
	(c) Kang, K.; Huang, L.; Weix, D. J. J. Am. Chem. Soc. 2020, 142, 10634. doi: 10.1021/jacs.0c04670 pmid: 32486635
[3]	(a) Nitta, Y.; Arakawa, Y. Chem. Pharm. Bull. 1985, 33, 1380. doi: 10.1248/cpb.33.1380
	(b) Kabalka, G. W.; Varma, M.; Varma, R. S. J. Org. Chem. 1986, 51, 2386. doi: 10.1021/jo00362a044
	(c) Yoshida, Y.; Sakakura, Y.; Aso, N.; Okada, S.; Tanabe, Y. Tetrahedron 1999, 55, 2183. doi: 10.1016/S0040-4020(99)00002-2
	(d) Martinelli, M. J.; Nayyar, N. K.; Moher, E. D.; Dhokte, U. P.; Pawlak, J. M.; Vaidyanathan, R. Org. Lett. 1999, 1, 447. doi: 10.1021/ol990658l
	(e) Das, B.; Reddy, V. S. Chem. Lett. 2004, 33, 1428. doi: 10.1246/cl.2004.1428
	(f) Xu, L.; Xia, C. Synth. Commun. 2004, 34, 1199. doi: 10.1081/SCC-120030306
	(g) Zhao, N.; Li, Y.; Wang, Y.; Wang, J. J. Sulfur Chem. 2006, 27, 427. doi: 10.1080/17415990600863752
	(h) Meshram, G. A.; Patil, V. D. Tetrahedron Lett. 2009, 50, 1117. doi: 10.1016/j.tetlet.2008.12.085
	(i) Zou, J.-P.; Wu, D.-D.; Luo, J.; Xing, Q.-J.; Luo, X.-B.; Dong, W.-H.; Luo, S.-L.; Du, H.-M.; Suib, S. L. ACS Catal. 2016, 6, 6861. doi: 10.1021/acscatal.6b01729
	(j) Jing, L.; Yu, X.; Guan, M.; Wu, X.; Wang, Q.; Wu, Y. Chem. Res. Chin. Univ. 2018, 34, 191. doi: 10.1007/s40242-018-7305-0
[4]	(a) Oliverio, M.; Costanzo, P.; Paonessa, R.; Nardi, M.; Pro-copio, A. RSC Adv. 2013, 3. pmid: 29977387
	(b) Lakrout, S.; K'Tir, H.; Amira, A.; Berredjem, M.; Aouf, N.-E. RSC Adv. 2014, 4, 16027. doi: 10.1039/C4RA01346H pmid: 29977387
	(c) Choi, J. H.; Lee, B. C.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 1277. doi: 10.1021/jo0161835 pmid: 29977387
	(d) Lei, A.; Singh, A.; Yi, H.; Zhang, G.; Bian, C.; Pei, P. Synlett 2017, 28, 1558. doi: 10.1055/s-0036-1588728 pmid: 29977387
	(e) Dong, W.-H.; Wu, D.-D.; Luo, J.-M.; Xing, Q.-J.; Liu, H.; Zou, J.-P.; Luo, X.-B.; Min, X.-B.; Liu, H.-L.; Luo, S.-L.; Au, C.-T. J. Catal. 2017, 349, 218. doi: 10.1016/j.jcat.2017.02.004 pmid: 29977387
	(f) Deruer, E.; Hamel, S.; Canesi, S. Beilstein J. Org. Chem. 2018, 14, 1203. doi: 10.3762/bjoc.14.101 pmid: 29977387
	(g) Mulina, O. M.; Ilovaisky, A. I.; Terent'ev, A. O. Eur. J. Org. Chem. 2018, 2018, 4648. doi: 10.1002/ejoc.201800838 pmid: 29977387
	(h) Ji, Y.-Z.; Li, H.-J.; Zhang, J.-Y.; Wu, Y.-C. Eur. J. Org. Chem. 2019, 2019, 1846. doi: 10.1002/ejoc.201900097 pmid: 29977387
	(i) Lin, Y.; Yi, W. Chin. J. Org. Chem. 2018, 38, 1207. (in Chinese) pmid: 29977387
	( 林雅玫, 易文斌, 有机化学, 2018, 38, 1207.) doi: 10.6023/cjoc201711036 pmid: 29977387
	(j) Huang, G.; Li, X.; Luo, J.; Luo, Z.; Tan, M. Chin. J. Org. Chem. 2019, 39, 617. (in Chinese) doi: 10.6023/cjoc201809030 pmid: 29977387
	( 黄国保, 李秀英, 罗金荣, 罗志辉, 谭明雄, 有机化学, 2019, 39, 617.) doi: 10.6023/cjoc201809030 pmid: 29977387
[5]	(a) Luo, Y.-C.; Pan, X.-J.; Yuan, G.-Q. Tetrahedron 2015, 71, 2119. doi: 10.1016/j.tet.2015.02.048 pmid: 34094332
	(b) Feng, M.-L.; Xi, L.-Y.; Chen, S.-Y.; Yu, X.-Q. Eur. J. Org. Chem. 2017, 2017, 2746. doi: 10.1002/ejoc.201700269 pmid: 34094332
	(c) Nematollahi, D.; Joudaki, M.; Khazalpour, S.; Pouladi, F. J. Electrochem. Soc. 2017, 164, G65. doi: 10.1149/2.1111706jes pmid: 34094332
	(d) Yan, M.; Kawamata, Y.; Baran, P. S. Chem. Rev. 2017, 117, 13230. doi: 10.1021/acs.chemrev.7b00397 pmid: 34094332
	(e) Yang, Q. L.; Li, Y. Q.; Ma, C.; Fang, P.; Zhang, X. J.; Mei, T. S. J. Am. Chem. Soc. 2017, 139, 3293. doi: 10.1021/jacs.7b01232 pmid: 34094332
	(f) Jiang, Y.; Xu, K.; Zeng, C. Chem. Rev. 2018, 118, 4485. doi: 10.1021/acs.chemrev.7b00271 pmid: 34094332
	(g) Zheng, M. W.; Yuan, X.; Cui, Y. S.; Qiu, J. K.; Li, G.; Guo, K. Org. Lett. 2018, 20, 7784. doi: 10.1021/acs.orglett.8b03191 pmid: 34094332
	(h) Kang, J. C.; Tu, Y. Q.; Dong, J. W.; Chen, C.; Zhou, J.; Ding, T. M.; Zai, J. T.; Chen, Z. M.; Zhang, S. Y. Org. Lett. 2019, 21, 2536. doi: 10.1021/acs.orglett.9b00263 pmid: 34094332
	(i) Zhang, L.; Hu, X. Chem. Sci. 2020, 11, 10786. doi: 10.1039/d0sc01445a pmid: 34094332
	(j) Yang, Q.-L.; Wang, X.-Y.; Weng, X.-J.; Yang, X.; Xu, X.-T.; Tong, X.; Fang, P.; Wu, X.-Y.; Mei, T.-S. Acta Chim. Sinica 2019, 77, 866. (in Chinese) doi: 10.6023/A19040135 pmid: 34094332
	( 杨启亮, 王向阳, 翁信军, 杨祥, 徐学涛, 童晓峰, 方萍, 伍新燕, 梅天胜, 化学学报, 2019, 77, 866.) doi: 10.6023/A19040135 pmid: 34094332
	(k) Wu, Y.; Xi, Y.; Zhao, M.; Wang, S. Chin. J. Org. Chem. 2018, 38, 2590. (in Chinese) doi: 10.6023/cjoc201804001 pmid: 34094332
	( 吴亚星, 席亚超, 赵明, 王思懿, 有机化学, 2018, 38, 2590.) doi: 10.6023/cjoc201804001 pmid: 34094332
	(l) Meng, Z.; Feng, C.; Xu, K. Chin. J. Org. Chem. 2021, 41, 2535. (in Chinese) doi: 10.6023/cjoc202012013 pmid: 34094332
	( 蒙泽银, 冯承涛, 徐坤, 有机化学, 2021, 41, 2590.) pmid: 34094332
	(m) Lian, F.; Xu, K. Chin. J. Org. Chem. 2020, 40, 3490. (in Chinese) doi: 10.6023/cjoc202000072 pmid: 34094332
	( 廉菲, 徐坤, 有机化学, 2020, 40, 3490.) doi: 10.6023/cjoc202000072 pmid: 34094332
[6]	Jiang, M.; Yuan, Y.; Wang, T.; Xiong, Y.; Li, J.; Guo, H.; Lei, A. Chem. Commun. 2019, 55, 13852. doi: 10.1039/C9CC07777D
[7]	(a) Liu, K.; Tang, S.; Huang, P.; Lei, A. Nat. Commun. 2017, 8, 775. doi: 10.1038/s41467-017-00873-1
	(b) Wen, J.; Shi, W.; Zhang, F.; Liu, D.; Tang, S.; Wang, H.; Lin, X. M.; Lei, A. Org. Lett. 2017, 19, 3131. doi: 10.1021/acs.orglett.7b01256
	(c) Tang, S.; Wang, S.; Liu, Y.; Cong, H.; Lei, A. Angew. Chem., Int. Ed. 2018, 57, 4737. doi: 10.1002/anie.v57.17
	(d) Fu, Z.; Hao, G.; Fu, Y.; He, D.; Tuo, X.; Guo, S.; Cai, H. Org. Chem. Front. 2020, 7, 590. doi: 10.1039/C9QO01139K
	(e) Hu, X.; Nie, L.; Zhang, G.; Lei, A. Angew. Chem., Int. Ed. 2020, 59, 15238. doi: 10.1002/anie.v59.35
[8]	Tian, Z.; Gong, Q.; Huang, T.; Liu, L.; Chen, T. J. Org. Chem. 2021, 86, 15914. doi: 10.1021/acs.joc.1c00260
[9]	Gromov, V. F.; Gerasimov, G. N.; Ikim, M. I.; Spiridonova, E. Y.; Trakhtenberg, L. I. Russ. J. Phys. Chem. B 2020, 14, 492. doi: 10.1134/S1990793120030045
[10]	Ramalingam, S.; Periandy, S.; Sugunakala, S.; Prabhu, T.; Bououdina, M. Spectrochim. Acta A 2013, 115, 118. doi: 10.1016/j.saa.2013.06.034
[11]	(a) Lu, F.; Li, J.; Wang, T.; Li, Z.; Jiang, M.; Hu, X.; Pei, H.; Yuan, F.; Lu, L.; Lei, A. Asian J. Org. Chem. 2019, 8, 1838. doi: 10.1002/ajoc.v8.10
	(b) Wu, Y. C.; Jiang, S. S.; Luo, S. Z.; Song, R. J.; Li, J. H. Chem. Commun. 2019, 55, 8995. doi: 10.1039/C9CC03789F
[12]	Alam, S.; Koo, S. Synth. Commun. 2018, 48, 247. doi: 10.1080/00397911.2017.1393088
[13]	Dond, B. D.; Thore, S. N. Tetrahedron Lett. 2020, 61, 151660. doi: 10.1016/j.tetlet.2020.151660
[14]	Munday, R. H.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem. Soc. 2008, 130, 2754. doi: 10.1021/ja711449e
[15]	Washio, T.; Nambu, H.; Anada, M.; Hashimoto, S. Tetrahedron: Asymmetry 2007, 18, 2606.
[16]	Feng, S.; Li, J.; Wei, J. New J. Chem. 2017, 41, 4743. doi: 10.1039/C7NJ00141J
[17]	Lee, C.; Ball, N. D.; Sammis, G. M. Chem. Commun. 2019, 55, 14753. doi: 10.1039/C9CC08487H
[18]	Bhatthula, B. K. G.; Subbarao, S. M. C. Synth. Commun. 2020, 4, 3133.
[19]	Takata, T.; Kim, Y. H.; Oae, S.; Suzuki, K. T. Tetrahedron Lett. 1978, 44, 4303. doi: 10.1016/S0040-4039(03)01064-5
[20]	Chandra, J.; Chaudhuri, R.; Manne, S. R.; Mondal, S.; Man-dal, B. ChemistrySelect 2017, 2, 8471. doi: 10.1002/slct.201701554

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