碘化钾催化无保护8-氨基喹啉的选择性C(5)-芳基硫醚化和C(5),C(7)-双芳基硫醚化及吲哚C(2),C(3)-双芳基硫醚化反应

doi:10.6023/cjoc202206029

摘要/Abstract

报道了采用2.5 mol%碘化钾为唯一催化剂, 无需任何过渡金属催条件下无保护8-氨基喹啉的碳-氢甲芳基硫醚化反应. 有趣的是, 通过简单调控反应时间和介质可以实现选择性的C(5)-芳基硫醚化和C(5),C(7)-双芳基硫醚化. 在对二甲苯中反应12 h时为C(5)-芳基硫醚化. 另一方面, 延长反应时间至24 h并更换反应介质为甲苯则选择性地发生C(5),C(7)-双芳基硫醚化. 此外, 双芳基硫醚化反应可以扩展到吲哚类底物, 实现含2,3-二芳基硫醚结构的吲哚合成.

关键词: 碳-氢键官能化, 自由基, 8-氨基喹啉, 选择性, 芳基硫醚化

The aromatic C—H sulfenylation reactions of unprotected 8-aminoquinolines have been realized by employing KI as the only catalyst at 2.5 mol% loading without using any transition metal reagent. Interestingly, the selective C(5)-sulfenylation and C(5),C(7)-disulfenylation have been successfully achieved by simply controlling the reaction time. Reaction time of 12 h in p-xylene enables the C(5)-sulfenylation. On the other hand, prolonging the reaction time to 24 h and switching the reaction medium to toluene lead to the selective C(5),C(7)-double sulfenylation. Moreover, the double sulfenylation has been extended to the indole substrate for the selective synthesis of 2,3-disulfenyl indoles.

Key words: C—H functionalization, free radical, 8-aminoquinoline, selectivity, sulfenylation

引用此文

吴豪志, 罗田, 姜建文, 万结平. 碘化钾催化无保护8-氨基喹啉的选择性C(5)-芳基硫醚化和C(5),C(7)-双芳基硫醚化及吲哚C(2),C(3)-双芳基硫醚化反应[J]. 有机化学, 2022, 42(11): 3721-3729.

Haozhi Wu, Tian Luo, Jianwen Jiang, Jieping Wan. KI-Catalyzed Selective C(5)-Sulfenylation and C(5),C(7)-Disulfenylation of Unprotected 8-Aminoquinolines and the Indole C(2),C(3)-Disulfenylation[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3721-3729.

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参考文献 17

[1]	(a) Bisht, R.; Haldar, C.; Hassan, M. M. M.; Hoque, M. E.; Chaturvedi, J.; Chattopadhyay, B. Chem. Soc. Rev. 2022, 51, 5042. doi: 10.1039/D1CS01012C
	(b) Liao, Y.; Liu, F.; Shi, Z.-J. Chem. Commun. 2021, 57, 13288. doi: 10.1039/D1CC04802C
	(b) Ali, R.; Siddiqui, R. Adv. Synth. Catal. 2021, 363, 1290. doi: 10.1002/adsc.202001053
	(d) Tian, S.; Luo, T.; Zhu, Y.; Wan, J.-P. Chin. Chem. Lett. 2020, 31, 3073. doi: 10.1016/j.cclet.2020.07.042
	(e) Zhao, B.; Liu, Y. Synthesis 2020, 52, 3211. doi: 10.1055/s-0040-1707124
	(f) Katariri, T.; Amao, Y. Green Chem. 2020, 22, 6682. doi: 10.1039/D0GC01796E
[2]	(a) Chen, Y.; Wen, S.; Tian, Q.; Zhang, Y.; Cheng, G. Org. Lett. 2021, 23, 7905. doi: 10.1021/acs.orglett.1c02912 pmid: 34085523
	(b) Yu, Q.; Liu, Y.; Wan, J.-P. Chin. Chem. Lett. 2021, 32, 3514. doi: 10.1016/j.cclet.2021.04.037 pmid: 34085523
	(c) Moseev, T. D.; Nikiforov, E. A.; Varaksin, M. V.; Charushin, V. N.; Chupakhin, O. N. J. Org. Chem. 2021, 86, 13702. doi: 10.1021/acs.joc.1c01796 pmid: 34085523
	(d) Selmani, A.; Schoenebeck, F. Org. Lett. 2021, 23, 4779. doi: 10.1021/acs.orglett.1c01505 pmid: 34085523
	(e) Han, Q.-Q.; Chen, D.-M.; Wang, Z.-L.; Sun, Y.-Y.; Yang, S.-H.; Song, J.-C.; Dong, D.-Q. Chin. Chem. Lett. 2021, 32, 2559. doi: 10.1016/j.cclet.2021.02.018 pmid: 34085523
	(f) Zhu, H.-L.; Zeng, F.-L.; Chen, X.-L.; Sun, K.; Li, H.-C.; Yuan, X.-Y.; Qu, L.-B.; Yu, B. Org. Lett. 2021, 23, 2976. doi: 10.1021/acs.orglett.1c00655 pmid: 34085523
	(g) Liu, D.; Zhang, Z.; Yu, J.; Chen, H.; Lin, X.; Li, M.; Wen, L.; Guo, W. Org. Chem. Front. 2022, 9, 2963. doi: 10.1039/D2QO00201A pmid: 34085523
	(h) Wang, Z.-Q.; Hou, C.; Zhong, Y.-F.; Lu, Y.-X.; Mo, Z.-Y.; Pan, Y.-M.; Tang, H.-T. Org. Lett. 2019, 21, 9841. doi: 10.1021/acs.orglett.9b03682 pmid: 34085523
[3]	(a) Nandy, A.; Kazi, I.; Guha, S.; Sekar, G. J. Org. Chem. 2021, 86, 2570. doi: 10.1021/acs.joc.0c02672 pmid: 29693382
	(b) Halimehjani, A. Z.; Shokrgozar, S.; Beier, P. J. Org. Chem. 2018, 83, 5778. doi: 10.1021/acs.joc.8b00206 pmid: 29693382
	(c) Guo, W.-S.; Gong, H.; Zhang, Y.-A.; Wen, L.-R.; Li, M. Org. Lett. 2018, 20, 6394. doi: 10.1021/acs.orglett.8b02697 pmid: 29693382
	(d) Hazarika, S.; Barman, P. ChemistrySelect 2020, 5, 11583. doi: 10.1002/slct.202002512 pmid: 29693382
	(e) Taninoto, K.; Ohkado, R.; Iida, H. J. Org. Chem. 2019, 84, 14980. doi: 10.1021/acs.joc.9b02422 pmid: 29693382
	(f) Bai, F.; Zhang, S.; Wei, L.; Liu, Y. Asian J. Org. Chem. 2018, 7, 371. doi: 10.1002/ajoc.201700677 pmid: 29693382
[4]	(a) Zhang, B.; Liu, D.; Sun, Y.; Zhang, Y.; Feng, J.; Yu, F. Org. Lett. 2021, 23, 3076. doi: 10.1021/acs.orglett.1c00751
	(b) Deng, L.; Liu, Y. ACS Omega 2018, 3, 11890. doi: 10.1021/acsomega.8b01946
	(c) Zhang, C.; Luo, J.; Zhang, J.; Chen, L.; Zhu, X.; Guo, M.; Shen, C.; Li, Z.; Wang, W. Asian J. Org. Chem. 2022, 11, e202200014.
	(d) Zhang, T.; Yao, W.; Wan, J.-P.; Liu, Y. Adv. Synth. Catal. 2021, 363, 4811. doi: 10.1002/adsc.202100617
	(e) Ali, D.; Panday, A. K.; Choudhury, L. H. J. Org. Chem. 2020, 85, 13610. doi: 10.1021/acs.joc.0c01738
	(e) Zeng, F.-L.; Zhu, H.-L.; Chen, X.-L.; Qu, L.-B.; Yu, B. Green Chem. 2021, 23, 3677. doi: 10.1039/D1GC00938A
[5]	(a) Zhao, F.; Tan, Q.; Wang, D.; Chen, J.; Deng, G.-J. Adv. Synth. Catal. 2019, 361, 4075. doi: 10.1002/adsc.201900666
	(b) Chen, L.; Xuchen, X.; Wang, F.; Yuang, Y.; Deng, G.; Liu, Y.; Liang, Y. Org. Biomol. Chem. 2021, 19, 10068. doi: 10.1039/D1OB01989A
	(b) Tian, S.; Wang, C.; Xia, J.; Wan, J.-P.; Liu, Y. Adv. Synth. Catal. 2021, 363, 4627. doi: 10.1002/adsc.202100816
	(c) Zhang, L.; Nagaraju, S.; Paplal, B.; Lin, Y.; Liu, S. Eur. J. Org. Chem. 2021, 1365.
	(d) Hu, B.; Zhang, Q.; Zhao, S.; Wang, Y.; Xu, L.; Yan, S.; Yu, F. Adv. Synth. Catal. 2019, 361, 49. doi: 10.1002/adsc.201801138
[6]	(a) Xu, Z.; Yang, X.; Yin, S.; Qiu, R. Top. Curr. Chem. 2020, 378, 42.
	(b) Khan, B.; Dutta, H. S.; Koley, D. Asian J. Org. Chem. 2018, 7, 1270. doi: 10.1002/ajoc.201800276
[7]	(a) Guo, X.; Li, P.; Wang, Q.; Wang, Q.; Wang, L. Org. Chem. Front. 2022, 9, 3192. doi: 10.1039/D1QO01912K
	(b) Wu, W.; Wu, M.; Yoshikai, N. Synthesis 2021, 53, 3144. doi: 10.1055/a-1337-5416
	(b) Zhang, Y.; Wen, C.; Li, J. Org. Biomol. Chem. 2018, 16, 1912. doi: 10.1039/C7OB03059B
	(c) Mondal, S.; Hajra, A. Org. Biomol. Chem. 2018, 16, 2846. doi: 10.1039/C8OB00537K
	(d) Zhao, L.; Li, P.; Xie, X.; Wang, L. Org. Chem. Front. 2018, 5, 1689. doi: 10.1039/C8QO00229K
[8]	(a) Lin, X.; Zeng, C.; Liu, C.; Fang, Z.; Guo, K. Org. Biomol. Chem. 2021, 19, 1352. doi: 10.1039/D0OB02055A
	(b) Wang, Y.; Wang, Y.; Jiang, K.; Zhang, Q.; Li, D. Org. Biomol. Chem. 2016, 14, 10180. doi: 10.1039/C6OB02079H
	(c) Du, Y.; Liu, Y.; Wan, J.-P. J. Org. Chem. 2018, 83, 3403. doi: 10.1021/acs.joc.8b00068
	(d) Hou, J.; Wang, K.; Zhang, C.; Wei, T.; Bai, R.; Xie, Y. Eur. J. Org. Chem. 2020, 6382.
	(e) Li, Y.; Zhu, L.; Cao, X.; Au, C.-T.; Qiu, R.; Yin, S.-F. Adv. Synth. Catal. 2017, 359, 2864. doi: 10.1002/adsc.201700391
[9]	(a) Dou, Y.; Xie, Z.; Sun, Z.; Fang, H.; Shen, C.; Zhang, P.; Zhu, Q. ChemCatChem 2016, 8, 3570. doi: 10.1002/cctc.201600874
	(b) Sheng, L.; Shen, D.; Zhu, J.; Wu, G.; Fan, G.; Wu, X.; Du, K. Tetrahedron 2021, 85, 132033. doi: 10.1016/j.tet.2021.132033
	(c) Ji, D.; He, X.; Xu, Y.; Xu, Z.; Bian, Y.; Liu, W.; Zhu, Q.; Xu, Y. Org. Lett. 2016, 18, 4478. doi: 10.1021/acs.orglett.6b01980
[10]	(a) Xia, C.; Wang, K.; Xu, J.; Shen, C.; Sun, D.; Li, H.; Wang, G.; Zhang, P. Org. Biomol. Chem. 2017, 15, 531. doi: 10.1039/C6OB02375D
	(b) Wen, C.; Zhong, R.; Qin, Z.; Zhao, M.; Li, J. Org. Biomol. Chem. 2020, 56, 9529.
	(c) Mondal, S.; Hajra, A. J. Org. Chem. 2018, 83, 11392. doi: 10.1021/acs.joc.8b01635
[11]	(a) Li, J.-M.; Weng, J.; Lu, G.; Chan, A. S. C. Tetrahedron Lett. 2016, 57, 2121.
	(b) Chen, G.; Zhang, X.; Zeng, Z.; Peng, W.; Liang, Y.; Liu, J. ChemistrySelect 2017, 2, 1979. doi: 10.1002/slct.201700235
	(c) Liu, X.; Zhang, H.; Yang, F.; Wang, B. Org. Biomol. Chem. 2019, 17, 7564. doi: 10.1039/C9OB01357A
	(d) Liang, S.; Manolikakes, G. M. Adv. Synth. Catal. 2016, 358, 2371. doi: 10.1002/adsc.201600388
[12]	Yu, Q.; Yang, Y.; Wan, J.-P.; Liu, Y. J. Org. Chem. 2018, 83, 11385. doi: 10.1021/acs.joc.8b01658
[13]	Kumar, V.; Banert, K.; Ray, D.; Saha, B. Org. Biomol. Chem. 2019, 17, 10245. doi: 10.1039/C9OB02235J
[14]	(a) Fu, L.; Wan, J.-P.; Zhou, Y.; Liu, Y. Chem. Commun. 2022, 58, 1808. doi: 10.1039/D1CC06768K
	(b) Luo, T.; Wu, H.; Liao, L.-h.; Wan, J.-P.; Liu, Y. J. Org. Chem. 2021, 86, 15785. doi: 10.1021/acs.joc.1c01851
	(c) Luo, T.; Tian, S.; Wan, J.-P.; Liu, Y. Curr. Org. Chem. 2021, 25, 1180.
[15]	(a) Pang, X.; Xiang, L.; Yang, X.; Yan, R. Adv. Synth. Catal. 2016, 358, 321. doi: 10.1002/adsc.201500943
	(b) Yang, Y.; Zhang, S.; Tang, L.; Hu, Y.; Zha, Z.; Wang, Z. Green Chem. 2016, 18, 26093.
	(c) Yang, F.-L.; Tian, S.-K. Angew. Chem., Int. Ed. 2013, 52, 4929. doi: 10.1002/anie.201301437
[16]	Lin, Y.-M.; Lu, G.-P.; Wang, G.-X.; Yi, W.-B. Adv. Synth. Catal. 2016, 358, 4100. doi: 10.1002/adsc.201600846
[17]	Chen, L.; Pu, J.; Liu, P.; Dai, B. J. Chem. Res. 2018, 42, 456. doi: 10.3184/174751918X15350179602459

Entry	Catalyst	Solvent	Temp./℃	Yield^b/%
Entry	Catalyst	Solvent	Temp./℃	3a	4a
1	KI	p-Xylene	120	36	0
2	TBAI	p-Xylene	120	36	0
3	I₂	p-Xylene	120	27	0
4	NIS	p-Xylene	120	33	0
5	NaI	p-Xylene	120	26	Trace
6^c	KI	p-Xylene	120	32	0
7^d	KI	p-Xylene	120	34	0
8	KI	p-Xylene	110	26	0
9	KI	p-Xylene	130	35	0
10	KI	Toluene	120	30	43
11	KI	DMF	120	25	0
12	KI	DMSO	120	0	0
13^e	KI	p-Xylene	120	32	0
14^f	KI	p-Xylene	120	60	Trace
15^g	KI	p-Xylene	120	52	0
16^h	KI	Toluene	120	Trace	57
17^h	KI	Toluene	110	21	43
18^h^,ⁱ	KI	Toluene	120	Trace	74
19^h^,^j	KI	Toluene	120	Trace	84
20^k	KI	Toluene	120	0	0
21	—	Toluene	120	0	0

Entry	Catalyst	Solvent	Temp./℃	Yield^b/%
Entry	Catalyst	Solvent	Temp./℃	3a	4a
1	KI	p-Xylene	120	36	0
2	TBAI	p-Xylene	120	36	0
3	I₂	p-Xylene	120	27	0
4	NIS	p-Xylene	120	33	0
5	NaI	p-Xylene	120	26	Trace
6^c	KI	p-Xylene	120	32	0
7^d	KI	p-Xylene	120	34	0
8	KI	p-Xylene	110	26	0
9	KI	p-Xylene	130	35	0
10	KI	Toluene	120	30	43
11	KI	DMF	120	25	0
12	KI	DMSO	120	0	0
13^e	KI	p-Xylene	120	32	0
14^f	KI	p-Xylene	120	60	Trace
15^g	KI	p-Xylene	120	52	0
16^h	KI	Toluene	120	Trace	57
17^h	KI	Toluene	110	21	43
18^h^,ⁱ	KI	Toluene	120	Trace	74
19^h^,^j	KI	Toluene	120	Trace	84
20^k	KI	Toluene	120	0	0
21	—	Toluene	120	0	0