Copper-Catalyzed Regioselective C(sp3)—H Sulfonimidization of Aliphatic Cyclic Tertiary Amines

doi:10.6023/cjoc202106035

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (11): 4459-4466.DOI: 10.6023/cjoc202106035 Previous Articles Next Articles

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铜催化脂肪族环状叔胺的区域选择性C(sp³)—H磺酰亚胺化

苟铨^a^,^*(), 谭秋健^a, 陈乾琼^a, 谭建红^a, 王凯民^c, 谢剑锋^b^,^*()

a 长江师范学院化学化工学院重庆 408100
b 中国科学院大学重庆市人民医院重庆 400013
c 云南民族大学化学与环境学院昆明 650500

收稿日期:2021-06-21 修回日期:2021-07-17 发布日期:2021-07-26
通讯作者: 苟铨, 谢剑锋
基金资助:
重庆市教育委员会研究(CXQT20026); 重庆市科学技术委员会基础研究与前沿探索(cstc2019jcyj-msxm1275); 涪陵区科学技术研究(FLKJ); 涪陵区科学技术研究(2019ABB2038); 重庆市教育委员会科学技术研究(KJQN202001403)

Copper-Catalyzed Regioselective C(sp³)—H Sulfonimidization of Aliphatic Cyclic Tertiary Amines

Quan Gou^a(), Qiujian Tan^a, Qianqiong Chen^a, Jianhong Tan^a, Kaimin Wang^c, Jianfeng Xie^b()

a School of Chemistry and Chemical Engineering, Yangtze Normal University, Chongqing 408100
b Department of Chongqing General Hospital, University of Chinese Academy of Sciences, Chongqing 400013
c School of Chemistry and Environment, Yunnan Minzu University, Chongqing 650500

Received:2021-06-21 Revised:2021-07-17 Published:2021-07-26
Contact: Quan Gou, Jianfeng Xie
Supported by:
Chongqing Municipal Education Commission(CXQT20026); Basic Research and Frontier Exploration of Science and Technology Commission of Chongqing(cstc2019jcyj-msxm1275); Fuling District Science and Technology(FLKJ); Fuling District Science and Technology(2019ABB2038); Science and Technology Research Program of Chongqing Municipal Education Commission(KJQN202001403)

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Abstract

This paper reports a concise and efficient synthesis method, namely copper-catalyzed direct hydrocarbon dehydrogenation coupling of sulfonamides and aliphatic cyclic tertiary amines, to realize the highly regioselective synthesis of (E)-N-sulfonylformamidines. The reaction is accomplished without any corrosive acid or base as an additive. It tolerates a broad scope of substrates, good functional group compatibility, and generates exclusive (E)-stereoselectivity. Moreover, this utility of the protocol is successfully demonstrated in a late-stage functionalization of medicinally active molecules and gram-scale synthesis.

Key words: copper catalysis, aliphatic cyclic tertiary amines, regioselective, sulfonylformamidines

Cite this article

Quan Gou, Qiujian Tan, Qianqiong Chen, Jianhong Tan, Kaimin Wang, Jianfeng Xie. Copper-Catalyzed Regioselective C(sp³)—H Sulfonimidization of Aliphatic Cyclic Tertiary Amines[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4459-4466.

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References 12

[1]	(a) Anglada, L.; Marquez, M.; Sacristan, A.; Oritiz, J. Eur. J. Med. Chem. 1988, 23, 97. doi: 10.1016/0223-5234(88)90174-2
	(b) Lee, M. Y.; Kim, M. H.; Kim, J.; Kim, J. K.; Kim, H.; Kim, B. T.; Jeong, I. H.; Chang, S.; Kim, S. H.; Chang, S.-Y. Bioorg. Med. Chem. Lett. 2010, 20, 541. doi: 10.1016/j.bmcl.2009.11.104
	(c) Vernier, W.; Chong, W.; Rewolinski, D.; Greasley, S.; Pauly, T.; Shaw, M.; Dinh, D.; Ferre, R. A.; Nukui, S.; Ornelas, M.; Reyner, E. Bioorg. Med. Chem. 2010, 18, 3307. doi: 10.1016/j.bmc.2010.03.014
	(d) Yamasaki, A.; Oda, Y.; Tanizaki, H.; Otsuka, T.; Fukunaga, A.; Nishigori, C.; Moriwaki, S. J. Cutan. Immunol. Allergy 2019, 2, 31. doi: 10.1002/cia2.2019.2.issue-1
	(e) Zheng, X.; Liu, Y.; Wan, J. -P. Chin. J. Org. Chem. 2020, 40, 1891. (in Chinese) doi: 10.6023/cjoc202003019
	(郑茜茜, 刘云云, 万结平, 有机化学, 2020, 40, 1891.) doi: 10.6023/cjoc202003019
[2]	Selected examples, see: (a) Oveston, R. G.; Steendam, R..; Jones, S.; Taylor, R. J. K. Org. Lett. 2012, 14, 1122. doi: 10.1021/ol300039x pmid: 27318119
	(b) Yang, L.; Zhao, Y.-L.; Zhao, C.-Y.; Li, H.-H.; Wang, M.-J.; Morris-Natschke, S.; Qian, K.; Lee, K.-H.; Liu, Y.-Q. Med. Chem. Res. 2014, 23, 5043. doi: 10.1007/s00044-014-1046-5 pmid: 27318119
	(c) Song, Z.; Chen, H.-L.; Wang, Y.-H.; Goto, M.; Gao, W.-J.; Cheng, P.-L.; Morris-Natschke, S. L.; Liu, Y.-Q.; Zhu, G.-X.; Wang, M.-J.; Lee, K.-H. Bioorg. Med. Chem. Lett. 2015, 25, 2690. doi: 10.1016/j.bmcl.2015.04.060 pmid: 27318119
	(d) Zhang, J.; Nan, X.; Yu, H.-T.; Cheng, P.-L.; Zhang, Y.; Liu, Y. Q.; Zhang, S. Y.; Hu, G.-F.; Liu, H.; Chen, A.-L. Eur. J. Med. Chem. 2016, 121, 422. doi: S0223-5234(16)30454-8 pmid: 27318119
	(e) Suja, T. D.; Divya, K. V. L.; Naik, L. V.; Kumar, A. R.; Kamal, A. Bioorg. Med. Chem. Lett. 2016, 26, 2072. doi: 10.1016/j.bmcl.2016.02.071 pmid: 27318119
	(f) Cornelio, B.; Laronze-Cochard, M.; Ceruso, M.; Ferraroni, M.; Rance, G. A.; Carta, F.; Khlobystov, A. N.; Fontana, A.; Supuran, C. T.; Sapi, J. J. Med. Chem. 2016, 59, 721. doi: 10.1021/acs.jmedchem.5b01771 pmid: 27318119
[3]	(a) Brasche, G.; Buchwald, S. L. Angew. Chem. Int. Ed. 2008, 47, 1932. doi: 10.1002/(ISSN)1521-3773
	(b) Wang, Y.-F.; Zhu, X.; Chiba, S. J. Am. Chem. Soc. 2012, 134, 3679. doi: 10.1021/ja2120629
	(c) McGowan, M. A.; McAvoy, C. Z.; Buchwald, S. L. Org. Lett. 2012, 14, 3800. doi: 10.1021/ol301700y
	(d) Wang, G.; Guo, Y.; Wan, J.-P. Chin. J. Org. Chem. 2020, 40, 645. (in Chinese) doi: 10.6023/cjoc201912018
	(王国栋, 郭艳辉, 万结平, 有机化学, 2020, 40, 645.) doi: 10.6023/cjoc201912018
[4]	(a) Oakley, S. H.; Soria, D. B.; Coles, M. P.; Hitchcock, P. B. Dalton Trans. 2004, 537.
	(b) Andersen, N. K.; Chandak, N.; Brulikova, L.; Kumar, P.; Jensen, M. D. F.; Sharma, P. K.; Nielsen, P. Bioorg. Med. Chem. 2010, 18, 4702. doi: 10.1016/j.bmc.2010.05.019
[5]	Selected reports, see: (a) Tang, X.; Wu, W.; Zeng, W.; Jiang, H. Acc. Chem. Res. 2018, 51, 1092. doi: 10.1021/acs.accounts.7b00611
	(b) Dhakshinamoorthy, A.; Asiri, A. M.; Garcia, H. ACS Catal. 2019, 9, 1081. doi: 10.1021/acscatal.8b04506
	(c) Zhu, C.; Yue, H.; Jia, J.; Rueping, M. Angew. Chem. Int. Ed. 2021, 60, 17810. doi: 10.1002/anie.v60.33
	(d) Dong, K.; Liu, Q.; Wu, L.-Z. Acta Chim. Sinica 2020, 78, 299. (in Chinese) doi: 10.6023/A19110412
	(董奎, 刘强, 吴骊珠, 化学学报, 2020, 78, 299.) doi: 10.6023/A19110412
	(e) Pei, P.; Zhang, F.; Yi, H.; Lei, A. Acta Chim. Sinica 2017, 75, 15. (in Chinese) doi: 10.6023/A16080417
	(裴朋昆, 张凡, 易红, 雷爱文, 化学学报, 2017, 75, 15.) doi: 10.6023/A16080417
	(f) Wu, Y.; Shi, B. Chin. J. Org. Chem. 2020, 40, 3517. (in Chinese) doi: 10.6023/cjoc202003057
	(吴勇杰, 史炳锋, 有机化学, 2020, 40, 3517.) doi: 10.6023/cjoc202003057
	(g) Ming, W.; Liu, X.; Mao, L.; Gu, X.; Ye, Q. Chin. J. Chem. 2021, 39, 1716. doi: 10.1002/cjoc.v39.6
	(h) Xi, L.; Shi, Z. Chin. J. Org. Chem. 2021, 41, 1264. (in Chinese) doi: 10.6023/cjoc202100021
	(席龙龙, 史壮志, 有机化学, 2021, 41, 1264.) doi: 10.6023/cjoc202100021
[6]	Bae, I.; Han, H.; Chang, S. J. Am. Chem. Soc. 2005, 127, 2038. doi: 10.1021/ja0432968
[7]	(a) Chow, S. Y.; Odell, L. R. J. Org. Chem. 2017, 82, 2515. doi: 10.1021/acs.joc.6b02894
	(b) Chen, J.; Long, W.; Fang, S.; Yang, Y.; Wan, X. Chem. Commun. 2017, 53, 13256. doi: 10.1039/C7CC07364J
	(c) Yang, W.; Huang, D.; Zeng, X.; Luo, D.; Wang, X.; Hu, Y. Chem. Commun. 2018, 54, 8222. doi: 10.1039/C8CC04699A
[8]	(a) Wang, S.; Wang, Z.; Zheng, X. Chem. Commun. 2009, 7372.
	(b) Xu, X.; Ge, Z.; Cheng, D.; Ma, L.; Lu, C.; Zhang, Q.; Yao, N.; Li, X. Org. Lett. 2010, 12, 897. doi: 10.1021/ol1000236
[9]	(a) Kim, J.; Lee, S. Y.; Lee, J.; Do, Y.; Chang, S. J. Org. Chem. 2008, 73, 9454. doi: 10.1021/jo802014g
	(b) Kim, J.; Stahl, S. S. J. Org. Chem. 2015, 80, 2448. doi: 10.1021/jo5029198
	(c) Ghasemi, Z.; Shojaei, S.; Shahrisa, A. RSC Adv. 2016, 6, 56213. doi: 10.1039/C6RA13251K
[10]	Gou, Q.; Liu, Z.; Cao, T.; Tan, X.; Shi, W.; Ran, M.; Cheng, F.; Qin, J. J. Org. Chem. 2020, 85, 2092. doi: 10.1021/acs.joc.9b02860
[11]	(a) Boess, E.; Sureshkumar, D.; Sud, A.; Wirtz, C.; Farès, C.; Klussmann, M. J. Am. Chem. Soc. 2011, 133, 8106. doi: 10.1021/ja201610c
	(b) Chen, J.; Liu, B.; Liu, D.; Liu, S.; Cheng, J. Adv. Synth. Catal. 2012, 354, 2438. doi: 10.1002/adsc.v354.13
[12]	Huang, B.; Yang, C.; Zhou, J.; Xia, W. Chem. Commun. 2020, 56, 5010. doi: 10.1039/C9CC09869K

Entry	Cat. Cu	Solvent	Additive	Yield^b/%
1	CuBr	PhCF₃	—	60
2	CuBr	DMF	—	40
3	CuBr	Mesitylene	—	87
4	CuBr	dioxane	—	42
5	—	Mesitylene	—	0
6	CuI	Mesitylene	—	0
7	Cu₂O	Mesitylene	—	Trace
8	CuCl	Mesitylene	—	92
9	Cu(OAc)₂	Mesitylene	—	20
10	CuCl₂	Mesitylene	—	83
11^c	CuCl	Mesitylene	—	0
12	CuCl	Mesitylene	Na₂CO₃	60
13	CuCl	Mesitylene	K₂CO₃	0
14^d	CuCl	Mesitylene	—	80

Entry	Cat. Cu	Solvent	Additive	Yield^b/%
1	CuBr	PhCF₃	—	60
2	CuBr	DMF	—	40
3	CuBr	Mesitylene	—	87
4	CuBr	dioxane	—	42
5	—	Mesitylene	—	0
6	CuI	Mesitylene	—	0
7	Cu₂O	Mesitylene	—	Trace
8	CuCl	Mesitylene	—	92
9	Cu(OAc)₂	Mesitylene	—	20
10	CuCl₂	Mesitylene	—	83
11^c	CuCl	Mesitylene	—	0
12	CuCl	Mesitylene	Na₂CO₃	60
13	CuCl	Mesitylene	K₂CO₃	0
14^d	CuCl	Mesitylene	—	80

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铜催化脂肪族环状叔胺的区域选择性C(sp³)—H磺酰亚胺化

Copper-Catalyzed Regioselective C(sp³)—H Sulfonimidization of Aliphatic Cyclic Tertiary Amines

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铜催化脂肪族环状叔胺的区域选择性C(sp3)—H磺酰亚胺化