单质硫: 合成含硫杂环的优质硫源

doi:10.6023/cjoc202109038

摘要/Abstract

含硫杂环化合物在药物、分子器件和材料等诸多领域应用广泛, 因而其合成方法备受关注. 合成含硫杂环的关键在于分子中C—S键的构建, 一般通过含硫有机物或无机物参与的C—H键功能化或C—X键偶联反应来实现. 单质硫价廉易得, 性质稳定, 是合成含硫杂环的优质硫原子供体, 因而以单质硫为原料合成含硫杂环成为人们研究的热点. 综述了近年来以单质硫为硫源合成各种含硫杂环的研究进展情况.

关键词: 含硫杂环, 单质硫, C—S键构建, 多组分串联反应

Sulfur-containing heterocyclic compounds are widely applied in many areas such as drugs, molecular devices and materials, etc., so their synthesis methods have attracted much attention. The key step for the synthesis of sulfur-containing heterocycles is the construction of C—S bond, which is generally realized by C—H bond functionalization or C—X bond coupling reaction with sulfur-containing organic or inorganic substances. Elemental sulfur is cheap, available and stable, and it is an excellent sulfur atom donor for the synthesis of sulfur-containing heterocycles. Therefore, the synthesis of sulfur-containing heterocycles from elemental sulfur has become a research hotspot. Herein, the recent research progress of synthesis of sulfur-containing heterocyclic employing sulfur as sulfur-source is reviewed.

Key words: sulfur-containing heterocycle, elemental sulfur, C—S bond construction, multi-component cascade reaction

引用此文

肖立伟, 刘光仙, 任萍, 吴彤桐, 卢玉伟, 孔洁. 单质硫: 合成含硫杂环的优质硫源[J]. 有机化学, 2022, 42(4): 1002-1012.

Liwei Xiao, Guangxian Liu, Ping Ren, Tongtong Wu, Yuwei Lu, Jie Kong. Elemental Sulfur: An Excellent Sulfur-Source for Synthesis of Sulfur-Containing Heterocyclics[J]. Chinese Journal of Organic Chemistry, 2022, 42(4): 1002-1012.

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[1]	(a) Cui, S. F.; Wan, Y.; Lv, J. S.; Damu, G. L. V.; Zhou, C. H. Sci. China Chem. 2012, 42, 1105. (in Chinese)
	( 崔胜峰, 王艳, 吕敬松, Damu, Guri, L. V.; 周成合; 中国科学: 化学, 2012, 42, 1105.)
	(b) He, W.; Liu, D.; Gan, X.; Zhang, J.; Liu, Z.; Yi, C.; Song, B. Chin. J. Org. Chem. 2019, 39, 2287. (in Chinese)
	( 何文静, 刘登曰, 甘秀海, 张建, 刘峥军, 易崇粉, 宋宝安, 有机化学. 2019, 39, 2287.)
[2]	(a) Xiao, L. W.; Xiao, S. Q.; Li, Z.; Jing, X. M.; Dai, F. C. Chemistry 2019, 82, 120. (in Chinese)
	( 肖立伟, 肖树强, 李政, 景学敏, 戴富才, 化学通报, 2019, 82, 120.)
	(b) Xiao, L. W.; Liu, G. X.; Jing, X. M.;Ren L. L.; Xiao, S. Q. Chem. Res. Appl. 2020, 32, 297. (in Chinese)
	( 肖立伟, 刘光仙, 景学敏, 任丽磊, 肖树强, 化学研究与应用, 2020, 32, 297.)
[3]	(a) Beletskaya, I. P.; Ananikov, V. P. Chem. Rev. 2011, 111, 1596. doi: 10.1021/cr100347k pmid: 21391564
	(b) Yang, W.; Zhang, M.; Chen, W.; Yang, X.; Feng, J. Chin. J. Org. Chem. 2020, 40, 4060. (in Chinese) doi: 10.6023/cjoc202005039 pmid: 21391564
	( 杨文超, 张明明, 陈旺, 杨小虎, 冯建国, 有机化学, 2020, 40, 4060.) pmid: 21391564
[4]	(a) Shen, C.; Zhang, P.; Sun, Q.; Bai, S.; Hor, T. S. A.; Liu, X. Chem. Soc. Rev. 2015, 44, 291. doi: 10.1039/C4CS00239C pmid: 33528480
	(b) Sundaravelu, N.; Sangeetha, S.; Sekar, G. Org. Biomol. Chem. 2021, 19, 1459. doi: 10.1039/d0ob02320e pmid: 33528480
[5]	(a) Nguyena, T. B. Adv. Synth. Catal. 2017, 359, 1066. doi: 10.1002/adsc.201601329
	(b) Li, J.; Yang, S.; Wu, W.; Jiang, H. Org. Chem. Front. 2020, 7, 1395. doi: 10.1039/D0QO00377H
	(c) Nguyen, T. B. Adv. Synth. Catal. 2020, 362, 3448. doi: 10.1002/adsc.202000535
	(d) Fan, R.; Tan, C.; Liu, Y.; Wei, Y.; Zhao, X.; Liu, X.; Tan, J.; Yoshida, H. Chin. Chem. Lett. 2021, 32, 299. doi: 10.1016/j.cclet.2020.06.003
	(e) Cheng, H.; Guo, P.; Chen, B.; Yao, J.; Ma, J.; Hu, W.; Ji, H. Chin. J. Org. Chem. 2021, 41, 94. (in Chinese) doi: 10.6023/cjoc202006032
	( 程辉成, 郭鹏虎, 陈冰, 姚嘉伟, 马姣丽, 胡炜杰, 纪红兵, 有机化学, 2021, 41, 94.)
[6]	(a) Colebourne, N.; Foster, R. G.; Robson, E. J. Chem. Soc. C 1967, 685.
	(b) Beck, G.; Heitzer, H.; Holtschmidt, H. Synthesis 1985, 586.
	(c) Gewald, V. K.; Böttcher, H.; Mayer, R. J. Prakt. Chem. 1964, 23, 298.
	(d) Gewald, V. K.; Spies, H.; Mayer, R. J. Prakt. Chem. 1970, 312, 776. doi: 10.1002/prac.19703120507
[7]	Deng, H.; Li, Z.; Ke, F.; Zhou, X. Chem.-Eur. J. 2012, 18, 4840. doi: 10.1002/chem.201103525
[8]	Yang, Z.; Hu, R.; Li, X.; Wang, X.; Gu, R.; Han, S. Tetrahedron Lett. 2017, 58, 2366. doi: 10.1016/j.tetlet.2017.05.004
[9]	Wang, R.; Ding, Y. l.; Liu, H.; Peng, S.; Ren, J.; Li, L. Tetrahedron Lett. 2014, 55, 945. doi: 10.1016/j.tetlet.2013.12.054
[10]	Xu, H.; Luo, C.; Li, Z.; Xiang, H.; Zhou, X. J. Heterocycl. Chem. 2015, 53, 120.
[11]	Huang, Y.; Yan, D.; Wang, X.; Zhou, P.; Wu, W.; Jiang, H. Chem. Commun. 2018, 54, 1742. doi: 10.1039/C7CC09855C
[12]	Huang, Y.; Zhou, P.; Wu, W.; Jiang, H. J. Org. Chem. 2018, 83, 2460. doi: 10.1021/acs.joc.7b03118
[13]	Pan, L.; Yu, L.; Wu, Z.; Li, Z.; Xiang, H.; Zhou, X. RSC Adv. 2015, 46, 27775.
[14]	Zhang, L. F.; Ni, Z. H.; Li, D. Y.; Qin, Z. H.; Wei, X. Y. Chin. Chem. Lett. 2012, 23, 281. doi: 10.1016/j.cclet.2011.12.004
[15]	Li, G.; Xie, H.; Chen, J.; Guo, Y.; Deng, G. J. Green Chem. 2017, 19, 4043. doi: 10.1039/C7GC01932G
[16]	Che, X.; Jiang, J.; Xiao, F.; Huang, H.; Deng, G. J. Org. Lett. 2017, 19, 4576. doi: 10.1021/acs.orglett.7b02168
[17]	Deng, G.; Jiang, J.; Li, G.; Zhang, F.; Xie, H. Adv. Synth. Catal. 2018, 360, 1622. doi: 10.1002/adsc.201701560
[18]	Zhang, J.; Zhao, X.; Liu, P.; Sun, P. J. Org. Chem. 2019, 84, 12596. doi: 10.1021/acs.joc.9b02145 pmid: 31502839
[19]	Zhu, X.; Zhou, F.; Yang, Y.; Deng, G.; Liang, Y. ACS Omega 2020, 5, 22, 13136.
[20]	Liu, Y.; Yuan, X.; Guo, X.; Zhang, X.; Chen, B. Tetrahedron 2018, 74, 6057. doi: 10.1016/j.tet.2018.08.047
[21]	Huynh, T. V.; Doan, K. V.; Luong, N. T. K.; Nguyen, D. T. P.; Doan, S. H.; Nguyen, T. T.; Phan, N. T. S. RSC Adv. 2020, 10, 18423. doi: 10.1039/D0RA01750G
[22]	Singh, M.; Vaishali, Paul, A. K.; Singh, V. Org. Biomol. Chem. 2020, 18, 4459. doi: 10.1039/D0OB00888E
[23]	Zhu, X.; Yang, Y.; Xiao, G.; Song, J.; Liang, Y.; Deng, G. Chem. Commun. 2017, 53, 11917. doi: 10.1039/C7CC07366F
[24]	Fu, R. G.; Wang, Y.; Xia, F.; Zhang, H. L.; Sun, Y.; Yang, D. W.; Wang, Y. W.; Yin, P. J. Org. Chem. 2019, 84, 12237. doi: 10.1021/acs.joc.9b02032
[25]	Nguyen, T. B.; Ermolenko, L.; Al-Mourabit, A. Org. Lett. 2013, 15, 4218. doi: 10.1021/ol401944a pmid: 23924277
[26]	Teramoto, M.; Imoto, M.; Takeda, M.; Mizuno, T.; Nomoto, A.; Ogawa, A. J. Org. Chem. 2020, 85, 15213. doi: 10.1021/acs.joc.0c02072
[27]	Nguyen, L. A.; Ngo, Q. A.; Retailleau, P.; Nguyen, T. B. Green Chem. 2017, 19, 4289. doi: 10.1039/C7GC01825H
[28]	Nguyen, T. B.; Ermolenko, L.; Retailleau, P.; Al-Mourabit, A. Angew. Chem., Int. Ed. 2014, 53, 13808. doi: 10.1002/anie.201408397
[29]	Tong, Y.; Pan, Q.; Jiang, Z.; Miao, D.; Shi, X.; Han, S. Tetrahedron Lett. 2014, 55, 5499. doi: 10.1016/j.tetlet.2014.08.037
[30]	Nguyen, T. B.; Pasturaud, K.; Ermolenko, L.; Al-Mourabit, A. Org. Lett. 2015, 17, 2562. doi: 10.1021/acs.orglett.5b01182 pmid: 25929738
[31]	Guntreddi, T.; Vanjari, R.; Singh, K. N. Org. Lett. 2015, 17, 976. doi: 10.1021/acs.orglett.5b00079
[32]	Xing, Q.; Ma, Y.; Xie, H.; Xiao, F.; Zhang, F.; Deng, G. J. J. Org. Chem. 2019, 84, 1238. doi: 10.1021/acs.joc.8b02619
[33]	Xu, Z.; Huang, H.; Chen, H.; Deng, G. J. Org. Chem. Front. 2019, 6, 3060. doi: 10.1039/C9QO00592G
[34]	Wang, X.; Qiu, X.; Wei, J.; Liu, J.; Song, S.; Wang, W.; Jiao, N. Org. Lett. 2018, 20, 2632. doi: 10.1021/acs.orglett.8b00840
[35]	Ni, P.; Tan, J.; Li, R.; Huang, H.; Zhang, F.; Deng, G. J. RSC Adv. 2020, 10, 3931. doi: 10.1039/C9RA09656F
[36]	Wu, M.; Jiang, Y.; An, Z.; Qi, Z.; Yan, R. Adv. Synth. Catal. 2018, 360, 4236. doi: 10.1002/adsc.201800693
[37]	Childers, K. K.; Haidle, A. M.; Machacek, M. R.; Rogers, J. P.; Romeo, E. Tetrahedron Lett, 2013, 54, 2506. doi: 10.1016/j.tetlet.2013.03.014
[38]	Ma, X.; Yu, X.; Huang, H.; Zhou, Y.; Song, Q. Org. Lett. 2020, 22, 5284. doi: 10.1021/acs.orglett.0c01275
[39]	Zhou, Z.; Liu, M.; Sun, S.; Yao, E.; Liu, S.; Wu, Z.; Yu, J. T.; Jiang, Y.; Cheng, J. Terahedron Lett. 2017, 58, 2571. doi: 10.1016/j.tetlet.2017.05.061
[40]	Wang, Z.; Xie, H.; Xiao, F.; Guo, Y.; Huang, H.; Deng, G. J. Eur. J. Org. Chem. 2017, 2017, 1604. doi: 10.1002/ejoc.201700148
[41]	Xie, H.; Cai, J.; Wang, Z.; Huang, H.; Deng, G. J. Org. Lett. 2016, 18, 2196. doi: 10.1021/acs.orglett.6b00806
[42]	Hagen, H.; Kohler, R. D.; Liebigs, H. F. Ann. Chem. 1980, 1216.
[43]	(a) Zhou, Z.; Liu, Y.; Chen, J.; Yao, E.; Cheng, J. Org. Lett. 2016, 18, 5268. doi: 10.1021/acs.orglett.6b02583
	(b) Chen, J.; Jiang, Y.; Yu, J. T.; Cheng, J. J. Org. Chem. 2016, 81, 271. doi: 10.1021/acs.joc.5b02280
[44]	Li, L.; Chen, Q.; Xu, H.; Zhang, X. H.; Zhang, X. G. J. Org. Chem. 2020, 85, 10083. doi: 10.1021/acs.joc.0c01334
[45]	Xie, H.; Li, G.; Zhang, F.; Xiao, F.; Deng, G. J. Green Chem. 2018, 20, 827. doi: 10.1039/C7GC03599C
[46]	Abdelwahab, A. B.; Hanna, A. G.; Kirsch, G. Synthesis 2016, 48, 2881. doi: 10.1055/s-0035-1561459
[47]	Huang, X. G.; Liu, J.; Ren, J.; Wang, T.; Chen, W.; Zeng, B. B. Tetrahedron, 2011, 67, 6202. doi: 10.1016/j.tet.2011.06.061
[48]	Akbarzadeh, A.; Dekamin, M. G. Green Chem. Lett. Rev. 2017, 10, 315. doi: 10.1080/17518253.2017.1380234
[49]	Treu, M.; Karner, T.; Kousek, R.; Berger, H.; Mayer, M.; McConnell, D. B.; Stadler, A. J. Comb. Chem. 2008, 10, 863. doi: 10.1021/cc800081b
[50]	Tayebee, R.; Ahmadi, S. J.; Seresht, E. R.; Javadi, F.; Yasemi, M. A.; Hosseinpour, M.; Maleki, B. Ind. Eng. Chem. Res. 2012, 51, 14577. doi: 10.1021/ie301737h
[51]	Bai, R.; Liu, P.; Yang, J.; Liu, C.; Gu, Y. ACS Sustainable Chem. Eng. 2015, 3, 1292. doi: 10.1021/sc500763q
[52]	Wang, Z.; Qu, Z.; Xiao, F.; Huang, H.; Deng, G. J. Adv. Synth. Catal. 2018, 360, 796. doi: 10.1002/adsc.201701332
[53]	Nguyen, T. T. T.; Le, V A. Adv. Synth. Catal. 2019, 362, 160. doi: 10.1002/adsc.201901235
[54]	Nguyen, T. B.; Retailleau, P. Green Chem. 2018, 20, 387. doi: 10.1039/C7GC03437G
[55]	Chithiravel, R.; Rajaguru, K.; Muthusubramanian, S.; Bhuvanesh, N. RSC Adv. 2015, 5, 86414. doi: 10.1039/C5RA17829K
[56]	Han, Y.; Tang, W. Q.; Yan, C. Tetrahedron Lett. 2014, 55, 1441.
[57]	Zhang, G.; Yi, H.; Chen, H.; Bian, C.; Liu, C.; Lei, A. Org. Lett. 2014, 16, 6156. doi: 10.1021/ol503015b
[58]	(a) Kasano, Y.; Okada, A.; Hiratsuka, D.; Oderaotoshi, Y.; Minakata, S.; Komatsu, M. Tetrahedron 2006, 62, 537. doi: 10.1016/j.tet.2005.10.024
	(b) Yang, S.CN 10654449, 2010.
[59]	Jin, S.; Kuang, Z.; Song, Q. Org. Lett. 2020, 22, 615. doi: 10.1021/acs.orglett.9b04389
[60]	Solovyev, A. Y.; Androsov, D. A.; Neckers, D. C. J. Org. Chem. 2007, 72, 3122. pmid: 17375954
[61]	Nguyen, T, B.; Retailleau, P. Org. Lett. 2017, 19, 4858. doi: 10.1021/acs.orglett.7b02321 pmid: 28840729
[62]	Jiang, P.; Che, X.; Liao, Y.; Huang, H.; Deng, G. J. RSC Adv. 2016, 47, 41751.
[63]	(a) Higashino, T.; Ueda, A.; Yoshida, J.; Mori, H. Chem. Commun. 2017, 53, 3426. doi: 10.1039/C7CC00784A
	(b) Hanekamp, J. C.; Klusener, P.; Brandsma, L. Synth. Commun 1989, 19, 2691. doi: 10.1080/00397918908053063
[64]	Nagahora, N.; Takemoto, I.; Fujii, M.; Shioji, K.; Okuma, K. Org. Lett. 2017, 19, 2110. doi: 10.1021/acs.orglett.7b00716
[65]	Moon, S.; Kato, M.; Nishii, Y.; Miura, M. Adv. Synth. Catal. 2020, 362, 1669. doi: 10.1002/adsc.202000112
[66]	(a) Sakai, S.; Sato, K.; Yoshida, K. Tetrahedron Lett. 2020, 61, 151476. doi: 10.1016/j.tetlet.2019.151476 pmid: 16323873
	(b) Meng, L.; Fujikawa, T.; Kuwayama, M.; Segawa, Y.; Itami, K. J. Am. Chem. Soc. 2016, 138, 10351. doi: 10.1021/jacs.6b06486 pmid: 16323873
	(c) Takimiya, K.; Konda, Y.; Ebata, H.; Niihara, N.; Otsubo, T. J. Org. Chem. 2005, 70, 10569. pmid: 16323873
	(d) Fedenok, L. G.; Fedotov, K. Y.; Pritchina, E. A.; Polyakov, N. E. Tetrahedron Lett. 2016, 57, 1273. doi: 10.1016/j.tetlet.2016.02.025 pmid: 16323873
	(e) Shoji, T.; Miura, K.; Ohta, A.; Sekiguchi, R.; Ito, S.; Endo, Y.; Nagahata, T.; Mori, S.; Okujima, T. Org. Chem. Front. 2019, 6, 2801. doi: 10.1039/c9qo00593e pmid: 16323873
[67]	Huang, H.; Xu, Z.; Ji, X.; Li, B.; Deng, G. J. Org. Lett. 2018, 20, 4917. doi: 10.1021/acs.orglett.8b02049
[68]	Zhou, P.; Huang, Y.; Wu, W.; Yu, W.; Li, J.; Zhu, Z.; Jiang, H. Org. Biomol. Chem. 2019, 17, 3424. doi: 10.1039/C9OB00377K
[69]	Huang, H.; Wang, Q.; Xu, Z.; Deng, G. J. Adv. Synth. Catal. 2019, 361, 591. doi: 10.1002/adsc.201801324
[70]	Pham, P. H.; Nguyen, K. X.; Pham, H. T. B.; Tran, T. T.; Nguyen, T. T.; Phan, N. T. S. RSC Adv. 2020, 10, 11024. doi: 10.1039/D0RA00808G
[71]	Huang, H.; Qu, Z.; Ji, X.; Deng, G. J. Org. Chem. Front. 2019, 6, 1146.
[72]	Zhou, P.; Huang, Y.; Wu, W.; Zhou, J.; Yu, W.; Jiang, H. Org. Lett. 2019, 21, 9976. doi: 10.1021/acs.orglett.9b03900
[73]	Zhang, W.; Tao, S.; Ge, H.; Li, Q.; Ai, Z.; Li, X.; Zhang, B.; Sun, F.; Xu, X.; Du, Y. Org. Lett. 2020, 22, 448. doi: 10.1021/acs.orglett.9b04206 pmid: 31894988
[74]	Pham, P. H.; Nguyen, K. X.; Pham, H. T. B.; Nguyen, T. T.; Phan, N. T. S. Org. Lett. 2019, 21, 8795. doi: 10.1021/acs.orglett.9b03414
[75]	Yue, Y.; Shao, H.; Wang, Z.; Wang, K.; Wang, L.; Zhuo, K.; Liu, J. J. Org. Chem. 2020, 85, 11265. doi: 10.1021/acs.joc.0c01363
[76]	Liu, J.; Zhang, Y.; Yue, Y.; Wang, Z.; Shao, H.; Zhuo, K.; Lv, Q.; Zhang, Z. J. Org. Chem. 2019, 84, 12946. doi: 10.1021/acs.joc.9b01586
[77]	Li, B.; Ni, P.; Huang, H.; Xiao, F.; Deng, G. J. Adv. Synth. Catal. 2017, 359, 4300. doi: 10.1002/adsc.201701106
[78]	Ni, P.; Li, B.; Huang, H.; Xiao, F.; Deng, G. J. Green Chem. 2017, 19, 5553. doi: 10.1039/C7GC02818K
[79]	Liao, Y.; Peng, Y.; Qi, H.; Deng, G. J.; Gong, H.; Li, C. Chem. Commun. 2015, 51, 1031. doi: 10.1039/C4CC08370A
[80]	Lu, C.; Huang, H.; Tuo, X.; Jiang, P.; Zhang, F.; Deng, G. J. Org. Chem. Front. 2019, 6, 2738. doi: 10.1039/C9QO00603F
[81]	Chitrala, T.; Rahman, N. K. F. Org Lett, 2020, 22, 1726. doi: 10.1021/acs.orglett.9b04598 pmid: 32057247
[82]	Xu, Z.; Deng, G. J.; Zhang, F.; Chen, H.; Huang, H. Org. Lett. 2019, 21, 8630. doi: 10.1021/acs.orglett.9b03241
[83]	Chen, J.; Li, G.; Xie, Y.; Liao, Y.; Xiao, F.; Deng, G. J. Org. Lett., 2015, 17, 5870. doi: 10.1021/acs.orglett.5b03058
[84]	Jiang, J.; Tuo, X.; Fu, Z.; Huang, H.; Deng, G. J. Org. Biomol. Chem. 2020, 18, 3234. doi: 10.1039/D0OB00074D
[85]	Nguyen, T. B.; Retailleau, P.; Org. Lett. 2018, 20, 186. doi: 10.1021/acs.orglett.7b03547 pmid: 29219319
[86]	Chen, F. J.; Liao, G.; Li, X.; Wu, J. Shi, B. F. Org. Lett. 2014, 16, 5644. doi: 10.1021/ol5027156
[87]	Zhang, B.; Liu, D.; Sun, Y.; Zhang, Y.; Feng, J.; Yu, F. Org. Lett. 2021, 23, 8, 3076. doi: 10.1021/acs.orglett.0c02793

Entry	R²-FG	Product	Cat./base	Reaction condition	Yield/%	Ref.
1	Aldehyde	2-Arylbenzothiazole	CuCl₂-Phen/K₂CO₃	H₂O, 100 ℃	52~96	[7]
2	Benzylchloride	2-Arylbenzothiazole	Cu(OAc)_2/Na₂CO₃	DMSO, 130 ℃	53~98	[8]
3	Benzylamine	2-Arylbenzothiazole	Cu(OAc)₂/DABCO	DMSO, 100 ℃	10~90	[9]
4	Benzylamine	2-Arylbenzothiazole	CuCl-Phen	H₂O, 100 ℃	60~88	[10]
5	Terminalalkyne	2-Benzylbenzothiazole	CuTC/DBU	MeCN/H₂O, 130 ℃	45~84	[11]
6	Terminalalkyne	2-Arylbenzothiazole	CuI-Phen/K₂CO₃	DMSO, 110 ℃	62~90	[11]
7	N-Tosylhydrazone	2-Arylbenzothiazole	CuSCN/DBU	DMSO, 110 ℃	63~84	[12]
8	N-Tosylhydrazone	2-Benzylbenzothiazole	CuI, CsF/DABCO	MeCN, 130 ℃	57~70	[12]
9	Quaternaryammonium	2-Alkylbenzothiazole	KOH	H₂O, 140 ℃	74~95	[13]

Entry	R²-FG	Product	Cat./base	Reaction condition	Yield/%	Ref.
1	Aldehyde	2-Arylbenzothiazole	CuCl₂-Phen/K₂CO₃	H₂O, 100 ℃	52~96	[7]
2	Benzylchloride	2-Arylbenzothiazole	Cu(OAc)_2/Na₂CO₃	DMSO, 130 ℃	53~98	[8]
3	Benzylamine	2-Arylbenzothiazole	Cu(OAc)₂/DABCO	DMSO, 100 ℃	10~90	[9]
4	Benzylamine	2-Arylbenzothiazole	CuCl-Phen	H₂O, 100 ℃	60~88	[10]
5	Terminalalkyne	2-Benzylbenzothiazole	CuTC/DBU	MeCN/H₂O, 130 ℃	45~84	[11]
6	Terminalalkyne	2-Arylbenzothiazole	CuI-Phen/K₂CO₃	DMSO, 110 ℃	62~90	[11]
7	N-Tosylhydrazone	2-Arylbenzothiazole	CuSCN/DBU	DMSO, 110 ℃	63~84	[12]
8	N-Tosylhydrazone	2-Benzylbenzothiazole	CuI, CsF/DABCO	MeCN, 130 ℃	57~70	[12]
9	Quaternaryammonium	2-Alkylbenzothiazole	KOH	H₂O, 140 ℃	74~95	[13]

Entry	Ar-FG	Product	Cat.	Reaction condition	Yield/%	Ref.
1	Methylaromatic	2-Arylbenzothiazole	—	275 ℃	15~74	[14]
2	Methylaromatic	2-Arylnaphthothiazole	—	275 ℃	41~50	[14]
3	2-Methylarene	2-Heteroarylbenzothiazole	NH₄I	NMP, air, 160 ℃	37~87	[15]
4	Arylaldehyde	2-Arylnaphtho[2,1-d]thiazole	NH₄I/4 Å MS	DMSO/PhCl, 140 ℃	61~98	[16]
5	Arylaldehyde	2-Arylbenzothiazole	KI	O₂, NMP, 150 ℃	40~79	[16]
6	Styrene	2-Benzylbenzothiazole	NH₄I	NMP, air, 140 ℃	63~88	[17]
7	Arylacetylene	2-Benzylbenzothiazole	NH₄I	NMP, air, 140 ℃	57~81	[17]
8	Ether	2-Aryl, alkylbenzothiazole	TBHP^b/KI	DMSO, air, 130 ℃	41~81	[18]
9	Aliphaticamine	2-Aryl, alkylbenzothiazole	sealed tube	DMSO, 140 ℃	42~90	[19]
10	Acetophenone	2-Arylbenzothiazole	I₂, TBAI^c	DMSO/PhCl, 140 ℃	40~81	[20]
11	Acetophenone	2-Aroylbenzothiazole	I₂,	DMSO/PhCl, 140 ℃	42~78	[21]
12	Isatin	2-(2'-Aminophenyl)benzothiaole	KI/4 Å MS	DMSO, 120 ℃	60~85	[22]

Entry	Ar-FG	Product	Cat.	Reaction condition	Yield/%	Ref.
1	Methylaromatic	2-Arylbenzothiazole	—	275 ℃	15~74	[14]
2	Methylaromatic	2-Arylnaphthothiazole	—	275 ℃	41~50	[14]
3	2-Methylarene	2-Heteroarylbenzothiazole	NH₄I	NMP, air, 160 ℃	37~87	[15]
4	Arylaldehyde	2-Arylnaphtho[2,1-d]thiazole	NH₄I/4 Å MS	DMSO/PhCl, 140 ℃	61~98	[16]
5	Arylaldehyde	2-Arylbenzothiazole	KI	O₂, NMP, 150 ℃	40~79	[16]
6	Styrene	2-Benzylbenzothiazole	NH₄I	NMP, air, 140 ℃	63~88	[17]
7	Arylacetylene	2-Benzylbenzothiazole	NH₄I	NMP, air, 140 ℃	57~81	[17]
8	Ether	2-Aryl, alkylbenzothiazole	TBHP^b/KI	DMSO, air, 130 ℃	41~81	[18]
9	Aliphaticamine	2-Aryl, alkylbenzothiazole	sealed tube	DMSO, 140 ℃	42~90	[19]
10	Acetophenone	2-Arylbenzothiazole	I₂, TBAI^c	DMSO/PhCl, 140 ℃	40~81	[20]
11	Acetophenone	2-Aroylbenzothiazole	I₂,	DMSO/PhCl, 140 ℃	42~78	[21]
12	Isatin	2-(2'-Aminophenyl)benzothiaole	KI/4 Å MS	DMSO, 120 ℃	60~85	[22]

Entry	Ar-FG	Product	Cat./base	Reaction condition	Yield%	Ref.
1	Methylhetarene	2-Hetarylbenzothiazole	—	120 ℃	37~85	[25]
2	Methylhetarene	2-Hetarylbenzothiazole	NH₄I	Sulfolane, 175 ℃	9~60	[26]
3	Benzaldehyde	2-Arylbenzothiazole	NMM	130 ℃	60~80	[27]
4	Benzylamine	2-Arylbenzothiazole	Pyridine	100 ℃	61~80	[28]
5	Aliphatic amine	2-Arylbenzothiazole	—	130 ℃	52~80	[29]
6	Acetophenone	2-Aroylbenzothiazole	NMM	120 ℃	52~92	[30]
7	Arylacetic acid	2-Arylbenzothiazole	NMM	110 ℃	46~75	[31]
8	Benzylic alcohol	2-Arylbenzothiazole	FeCl₃/KHCO₃/NH₄I	NMP, 160 ℃	25~80	[32]