Electrochemical Synthesis of N-Acyl/Sulfonylsulfenamides Using Potassium Iodide as Mediator

doi:10.6023/cjoc202205026

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (11): 3730-3739.DOI: 10.6023/cjoc202205026 Previous Articles Next Articles

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碘化钾介导的电催化N-酰基/磺酰基次磺酰胺的合成

魏兆鑫, 王仁杰, 张永红, 王斌, 夏昱, 金伟伟^*(), 刘晨江^*()

新疆大学化学学院乌鲁木齐 830017

收稿日期:2022-05-18 修回日期:2022-07-01 发布日期:2022-07-20
通讯作者: 金伟伟, 刘晨江
基金资助:
国家自然科学基金(21702175); 国家自然科学基金(21961037); 国家自然科学基金(22161044); 新疆维吾尔自治区天山创新团队(2021D14011); 新疆维吾尔自治区自然科学基金(2020D01C077)

Electrochemical Synthesis of N-Acyl/Sulfonylsulfenamides Using Potassium Iodide as Mediator

Zhaoxin Wei, Renjie Wang, Yonghong Zhang, Bin Wang, Yu Xia, Weiwei Jin(), Chenjiang Liu()

College of Chemistry, Xinjiang University, Urumqi 830017

Received:2022-05-18 Revised:2022-07-01 Published:2022-07-20
Contact: Weiwei Jin, Chenjiang Liu
Supported by:
National Natural Science Foundation of China(21702175); National Natural Science Foundation of China(21961037); National Natural Science Foundation of China(22161044); Program for Tianshan Innovative Research Team of Xinjiang Uygur Autonomous Region(2021D14011); Natural Science Foundation of Xinjiang Uygur Autonomous Region(2020D01C077)

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Abstract

An efficient and environmentally friendly electrocatalytic protocol has been developed for synthesizing N-acyl/ sulfonyl sulfenamides. In an undivided cell, various electron-deficient groups substituted amines and aryl thiols react smoothly to afford the N—S bond formation products in 36%~98% yields. Preliminary mechanistic studies indicate that the reaction may work through a free radical process.

Key words: electrosynthesis, N—S bond formation, sulfenamides, cross coupling hydrogen evolution reaction

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Zhaoxin Wei, Renjie Wang, Yonghong Zhang, Bin Wang, Yu Xia, Weiwei Jin, Chenjiang Liu. Electrochemical Synthesis of N-Acyl/Sulfonylsulfenamides Using Potassium Iodide as Mediator[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3730-3739.

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Fig. & Tab. 9

Figure 1. Selected examples of sulfenamides

Scheme 1. Synthesis of electron-deficient sulfenamides

Entry	Variation from the standard conditions	Yield^b/%
1	None	98
2	KBr instead of KI	90
3	KCl instead of KI	13
4	NaBr instead of KI	87
5	NaI instead of KI	88
6	TBAI instead of KI	48
7	ⁿBu₄NBF₄ instead of KI	n.d.
8	15-Crown-5 instead of 18-crown-6	50
9	Dibenzo-18-crown-6 instead of 18-crown-6	46
10	MeOH instead of CH₂Cl₂	21
11	MeCN instead of CH₂Cl₂	69
12	DMF instead of CH₂Cl₂	70
13	Pt(＋)/Pt(－) instead of Pt(＋)/Ni(－)	94
14	C(＋)/Ni(－) instead of Pt(＋)/Ni(－)	72
15	Without 18-crown-6	n.d.
16	Without KI	n.d.
17	Without electric current	n.d.

Table 1. Optimization of reaction conditionsa

Table 2. Substrate scope of thiolsa

Table 3. Substrate scope of amidesa

Scheme 2. Mechanistic studies

Figure 2. (a) EPR measurement of a solution of KI and 18- crown-6 in CH2Cl2 in the presence of DMPO under constant- current conditions for 10 min; (b) EPR measurement of 1a under the same reaction conditions

Figure 3. Cyclic voltammetry of 1a and 2a in CH2Cl2 with KI (0.04 mol/L) and 18-crown-6 (0.04 mol/L) under air The glassy carbon-disk (R=5.5 mm, h=10 mm) was used as the working electrode. The Pt disk (R=5.5 mm, h=10 mm) and Ag/AgCl (R=5.0 mm, h=10 mm) was used as counter and reference electrode, respectively. The scan rate was 100 mV/s.

Scheme 3. Proposed mechanism

References 15

[1]	(a) Bowman, W. R.; Clark, D. N.; Marmon, R. J. Tetrahedron 1994, 50, 1275. doi: 10.1016/S0040-4020(01)80837-1 pmid: 17604170
	(b) Matsuo, J. I.; Iida, D.; Yamanaka, H.; Mukaiyama, T. Tetrahedron 2003, 59, 6739. doi: 10.1016/S0040-4020(03)00479-4 pmid: 17604170
	(c) Heldreth, B.; Long, T. E.; Jang, S.; Reddy, G.; Turos, E.; Dickey, S.; Lim, D. V. Bioorg. Med. Chem. 2006, 14, 3775. pmid: 17604170
	(d) Guarino, V. R.; Karunaratne, V.; Stella, V. J. Bioorg. Med. Chem. Lett. 2007, 17, 4910. pmid: 17604170
	(e) Aota, Y.; Kano, T.; Maruoka, K. Angew. Chem., Int. Ed. 2019, 58, 17661. doi: 10.1002/anie.201911021 pmid: 17604170
[2]	Craine, L.; Raban, M. Chem. Rev. 1989, 89, 689. doi: 10.1021/cr00094a001
[3]	Steinkamp, A. D.; Schmitt, L.; Chen, X.; Fietkau, K.; Heise, R.; Baron, J. M.; Bolm, C. Skin Pharmacol. Phys. 2016, 29, 281.
[4]	Guarino, V. R.; Olson, R. E.; Everlof, J. G.; Wang, N.; McDonald, I.; Haskell, R.; Clarke, W.; Lentz, K. A. Bioorg. Med. Chem. Lett. 2020, 30, 126856. doi: 10.1016/j.bmcl.2019.126856
[5]	Petkowski, J. J.; Bains, W.; Seager, S. Astrobiology 2018, 19, 579. doi: 10.1089/ast.2018.1831
[6]	(a) Barton, D. H. R.; Hesse, R. H.; O'Sullivan, A. C.; Pechet, M. M. J. Org. Chem. 1991, 56, 6702. doi: 10.1021/jo00023a040
	(b) Bao, M.; Shimizu, M.; Shimada, S.; Tanaka, M. Tetrahedron 2003, 59, 303. doi: 10.1016/S0040-4020(02)01554-5
[7]	Zhang, X.-S.; Zhang, X.-H. Phosphorus, Sulfur Silicon Relat. Elem. 2016, 191, 89. doi: 10.1080/10426507.2015.1012670
[8]	Lee, C.; Lim, Y. N.; Jang, H.-Y. Eur. J. Org. Chem. 2015, 5934.
[9]	(a) Torii, S.; Tanaka, H.; Ukida, M. J. Org. Chem. 1979, 44, 1554. doi: 10.1021/jo01323a039
	(b) Li, C.-J. Acc. Chem. Res. 2009, 42, 335. doi: 10.1021/ar800164n
	(c) Girard, S. A..; Knauber, T..; Li, C.-J. Angew. Chem., Int. Ed. 2014, 53, 74.
	(d) Wang, H.; Zhang, J.; Tan, J.; Xin, L.; Li, Y.; Zhang, S.; Xu, K. Org. Lett. 2018, 20, 2505. doi: 10.1021/acs.orglett.8b00165
	(e) Mo, Z.-Y.; Swaroop, T. R.; Tong, W.; Zhang, Y.-Z.; Tang, H.-T.; Pan, Y.-M.; Sun, H.-B.; Chen, Z.-F. Green Chem. 2018, 20, 4428. doi: 10.1039/C8GC02143K
	(f) Deng, L.; Wang, Y.; Mei, H.; Pan, Y.; Han, J. J. Org. Chem. 2019, 84, 949. doi: 10.1021/acs.joc.8b02882
	(g) Li, Y.; Yang, Q.; Yang, L.; Lei, N.; Zheng, K. Chem. Commun. 2019, 55, 4981. doi: 10.1039/C9CC01378D
	(h) Tang, S.; Liu, Y.; Li, L.; Ren, X.; Li, J.; Yang, G.; Li, H.; Yuan, B. Org. Biomol. Chem. 2019, 17, 1370. doi: 10.1039/C8OB03211D
	(i) Meng, Z.-Y.; Feng, C.-T.; Zhang, L.; Yang, Q.; Chen, D.-X.; Xu, K. Org. Lett. 2021, 23, 4214. doi: 10.1021/acs.orglett.1c01161
	(j) Deng, Y.; You, S.; Ruan, M.; Wang, Y.; Chen, Z.; Yang, G.; Gao, M. Adv. Synth. Catal. 2021, 363, 464. doi: 10.1002/adsc.202000997
	(k) Tian, Z.; Gong, Q.; Huang, T.; Liu, L.; Chen, T. J. Org. Chem. 2021, 86, 15914. doi: 10.1021/acs.joc.1c00260
	(l) Du, Z.; Qi, Q.; Gao, W.; Ma, L.; Liu, Z.; Wang, R.; Chen, J. Chem. Rec. 2021, 22, e202100178.
	(m) Li, J.; Zhang, S.; Xu, K. Chin. Chem. Lett. 2021, 32, 2729. doi: 10.1016/j.cclet.2021.03.027
[10]	(a) Li, W.-C.; Zeng, C.-C.; Hu, L.-M.; Tian, H.-Y.; Little, R. D. Adv. Synth. Catal. 2013, 355, 2884. doi: 10.1002/adsc.201300502
	(b) Liang, S.; Zeng, C.-C.; Tian, H.-Y.; Sun, B.-G.; Luo, X.-G.; Ren, F.-Z. Adv. Synth. Catal. 2018, 360, 1444. doi: 10.1002/adsc.201701401
	(c) Zhang, H. H.; Wang, Y. Q.; Huang, L. T.; Zhu, L. Q.; Feng, Y. Y.; Lu, Y. M.; Zhao, Q. Y.; Wang, X. Q.; Wang, Z. Chem. Commun. 2018, 54, 8265. doi: 10.1039/C8CC04471F
	(d) Sun, C.-C.; Lian, F.; Xu, K.; Zeng, C.-C.; Sun, B.-G. Adv. Synth. Catal. 2019, 361, 4041. doi: 10.1002/adsc.201900537
	(e) Zhang, S.; Li, L.; Xue, M.; Zhang, R.; Xu, K.; Zeng, C. Org. Lett. 2018, 20, 3443. doi: 10.1021/acs.orglett.8b00981
	(f) Li, Y.; Sun, C.-C.; Zeng, C.-C. J. Electroanal. Chem. 2020, 861, 113941. doi: 10.1016/j.jelechem.2020.113941
	(g) Huynh, T. N. T.; Tankam, T.; Koguchi, S.; Rerkrachaneekorn, T.; Sukwattanasinitt, M.; Wacharasindhu, S. Green Chem. 2021, 23, 5189. doi: 10.1039/D1GC01131F
	(h) Lian, F.; Xu, K.; Zeng, C. Chem. Rec. 2021, 21, 2290. doi: 10.1002/tcr.202100036
[11]	Sawamura, T.; Takahashi, K.; Inagi, S.; Fuchigami, T. Angew. Chem., Int. Ed. 2012, 51, 4413. doi: 10.1002/anie.201200438
[12]	Wei, Z.; Wang, R.; Zhang, Y.; Wang, B.; Xia, Y.; Abdukader, A.; Xue, F.; Jin, W.; Liu, C. Eur. J. Org. Chem. 2021, 4728.
[13]	(a) Dong, X.; Wang, R.; Jin, W.; Liu, C. Org. Lett. 2020, 22, 3062. doi: 10.1021/acs.orglett.0c00814
	(b) Wang, R.; Dong, X.; Zhang, Y.; Wang, B.; Xia, Y.; Abdukader, A.; Xue, F.; Jin, W.; Liu, C. Chem.-Eur. J. 2021, 27, 14931. doi: 10.1002/chem.202102262
	(c) Cheng, Z.; Gao, X.; Yao, L.; Wei, Z.; Qin, G.; Zhang, Y.; Wang, B.; Xia, Y.; Abdukader, A.; Xue, F.; Jin, W.; Liu, C. Eur. J. Org. Chem. 2021, 3743.
[14]	(a) Jin, W.; Zheng, P.; Wong, W.-T.; Law, G.-L. Adv. Synth. Catal. 2017, 359, 1588. doi: 10.1002/adsc.201601065 pmid: 31675240
	(b) Cheng, Z.; Jin, W.; Liu, C. Org. Chem. Front. 2019, 6, 841. doi: 10.1039/c8qo01412d pmid: 31675240
	(c) Cheng, Z.; Sun, P.; Tang, A.; Jin, W.; Liu, C. Org. Lett. 2019, 21, 8925. doi: 10.1021/acs.orglett.9b03192 pmid: 31675240
	(d) Chen, Z.; Jin, W.; Xia, Y.; Zhang, Y.; Xie, M.; Ma, S.; Liu, C. Org. Lett. 2020, 22, 8261. doi: 10.1021/acs.orglett.0c02907 pmid: 31675240
[15]	Kost, D.; Zeichner, A. Tetrahedron Lett. 1975, 16, 3239. doi: 10.1016/S0040-4039(00)91466-7

碘化钾介导的电催化N-酰基/磺酰基次磺酰胺的合成

Electrochemical Synthesis of N-Acyl/Sulfonylsulfenamides Using Potassium Iodide as Mediator

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Fig. & Tab. 9

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