碘催化乙烯基叠氮与芳基亚磺酸钠反应合成β-磺酰基烯胺

doi:10.6023/cjoc202106012

摘要/Abstract

发展了一种使用廉价碘单质作为催化剂, 乙烯基叠氮作为自由基受体, 芳基亚磺酸钠作为自由基源, 合成Z型结构的N-未保护的β-磺酰基烯胺类化合物的方法. 该反应中乙醇作为溶剂, 双三氟甲烷磺酰亚胺(Tf₂NH)作为添加剂, 在40 ℃下反应4~6 h, 可以以优良的产率得到β-磺酰基烯胺类化合物. 该方法无需使用金属催化剂, 具有条件简单、反应时间短、底物适用范围广等优点.

关键词: 碘催化, 乙烯基叠氮, 自由基加成, 磺酰基烯胺

The present protocol provides the facile and highly efficient synthesis of various Z-structure N-unprotected β-sulfonyl enamine compounds in a manner by using inexpensive molecular iodine as catalyst, vinyl azides as free radical acceptor, and sodium arylsulfinates as free radical sources. In this reaction, ethanol was used as solvent and bistrifluoromethanesulfonimide (Tf₂NH) was used as additive. The reaction was carried out at 40 ℃ for 4~6 h to obtain β-sulfonyl enamine compounds with good yields. The method does not need to use metal catalyst, and has the advantages of simple conditions, short reaction time and wide substrate application range.

Key words: iodine catalysis, vinyl azide, free radical addition, sulfonyl enamine

引用此文

刘锐凯, 许峥, 宁志涛, 杜正银. 碘催化乙烯基叠氮与芳基亚磺酸钠反应合成β-磺酰基烯胺[J]. 有机化学, 2022, 42(1): 200-207.

Ruikai Liu, Zheng Xu, Zhitao Ning, Zhengyin Du. Synthesis of β-Sulfonyl Enamines via Iodine-Catalyzed Reaction between Vinyl Azides and Sodium Arylsulfinates[J]. Chinese Journal of Organic Chemistry, 2022, 42(1): 200-207.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 7

图式1. β-磺酰基烯胺的合成方法

Scheme 1. Synthetic methods of β-sulfonyl enamines

Entry	Catalyst	Additive	Solvent	Yield^b/%
1	I₂	—	EtOH	53
2	—	—	EtOH	N.R.
3	I₂	—	H₂O	31
4	I₂	—	DCM	16
5	I₂	—	MeCN	17
6	I₂	—	MeOH	40
7	I₂	TsOH	EtOH	69
8	I₂	TfOH	EtOH	66
9	I₂	BF₃•Et₂O	EtOH	43
10	I₂	Tf₂NH	EtOH	81
11	I₂	Cu(OTf)₂	EtOH	77
12^c	I₂	Tf₂NH	EtOH	38
13^d	I₂	Tf₂NH	EtOH	Trace
14^e	I₂	Tf₂NH	EtOH	73
15^f	I₂	Tf₂NH	EtOH	79

表1. 乙烯基叠氮和芳基亚磺酸钠反应的条件优化

Table 1. Optimization of reaction conditions between vinyl azide and sodium aryl-sulfinate

表2. α-苯基乙烯基叠氮化合物的底物拓展a,b

Table 2. Scope of α-phenylvinyl azides

表3. 芳基亚磺酸钠的底物拓展a,b

Table 3. Scope of sodium arylsulfinates

图式2. N-未保护烯胺的产物转化

Scheme 2. Synthetic transformation of N-unprotected enamines

Reaction conditions	Yield/% of 3aa
Standard condition	81
No I₂	0
NIS (3 equiv.) instead of I₂	73
NIS (4 equiv.) instead of I₂	68
Under N₂atmosphere	76
Add TEMPO (3 equiv.)	Trace

表4. 控制实验

Table 4. Control experiments

图式3. 合成Z-β-磺酰基烯胺的可能机理

Scheme 3. Possible mechanism for the synthesis of Z-β-sulfonyl enamines

参考文献 38

[1]	Gu, P.; Su, Y.; Li, R. Org. Lett. 2012, 14, 2246. doi: 10.1021/ol3006437
[2]	Liu, Z.; Liao, P.; Bim, X. Org. Lett. 2014, 16, 3668. doi: 10.1021/ol501661k
[3]	Li, X.; Liao, S.; Zhang, L. Org. Lett. 2017, 19, 3687. doi: 10.1021/acs.orglett.7b01359
[4]	(a) Forster, M.; Newman, S. J. Chem. Soc. 1910, 97, 2570. doi: 10.1039/CT9109702570
	(b) Forster, M.; Newman, S. J. Chem. Soc. 1911, 99, 1277. doi: 10.1039/CT9119901277
[5]	Naresh Kumar Reddy, N.; Nageswara Rao, S.; Ravi, C.; Adimurthy, S. ACS Omega 2017, 2, 5235. doi: 10.1021/acsomega.7b00969 pmid: 31457795
[6]	Zhu, Z.; Tang, X.; Jiang, H. Org. Lett. 2017, 19, 1370. doi: 10.1021/acs.orglett.7b00203
[7]	Lei, W.; Wang, T.; Feng, K.; Wu, L.; Liu, Q. ACS Catal. 2017, 7, 7941. doi: 10.1021/acscatal.7b02818
[8]	Liu, Z.; Zhang, Z.; Zhu, G.; Zhou, Y.; Yan, L.; Gao, W.; Tong, L.; Tang, B. Org. Lett. 2019, 21, 7324. doi: 10.1021/acs.orglett.9b02616
[9]	Dey, R.; Banerjee, P. Org. Lett. 2017, 19, 304. doi: 10.1021/acs.orglett.6b03276
[10]	Wang, Y.; Hu, M.; Hayashi, H.; Xing, B.; Chiba, S. Org. Lett. 2016, 18, 992. doi: 10.1021/acs.orglett.6b00116
[11]	Lopez, E.; Lopez, L. Angew. Chem., nt. Ed. 2017, 56, 5121.
[12]	Rasool, F.; Ahmed, A.; Hussain, N.; Yousuf, S.; Mukherjee, D. Org. Lett. 2018, 20, 4036. doi: 10.1021/acs.orglett.8b01602
[13]	Das, D.; Kannaujiya, V.; Sadhu, M.; Ray, S.; Singh, V. J. Org. Chem. 2019, 84, 15865. doi: 10.1021/acs.joc.9b02127
[14]	Studer, A.; Curran, D. Angew. Chem., nt. Ed. 2016, 55, 58.
[15]	Sun, X.; Yu, S. Chem. Commun. 2016, 52, 10898. doi: 10.1039/C6CC05756J
[16]	Lei, W.; Feng, K.; Wang, T.; Wu, L.; Liu, Q. Org. Lett. 2018, 20, 7220. doi: 10.1021/acs.orglett.8b03147
[17]	Tang, P.; Zhang, C.; Chen, E.; Chen, B.; Chen, W.; Yu, Y. Tetrahedron Lett. 2017, 58, 2157. doi: 10.1016/j.tetlet.2017.04.069
[18]	Ning, Y.; Ji, Q.; Liao, P.; Anderson, E.; Bi, X. Angew. Chem., nt. Ed. 2017, 56, 13805.
[19]	Jung, H.; Kim, D. Synth. Commun. 2020, 50, 380. doi: 10.1080/00397911.2019.1696364
[20]	Banert, V. Angew. Chem., nt. Ed. 1985, 97, 231.
[21]	Wang, D.; Zhang, R.; Lin, S.; Deng, R.; Yan, Z. Chin. J. Org. Chem. 2016, 36, 2757. (in Chinese) doi: 10.6023/cjoc201604056
	(王丁意, 张荣兴, 林森, 邓瑞红, 严兆华, 有机化学, 2016, 36, 2757.) doi: 10.6023/cjoc201604056
[22]	(a) Mulina, O.; Ilovaisky, A.; Parshin, V.; Terent'ev, A. Adv. Synth. Catal. 2020, 362, 4579. doi: 10.1002/adsc.v362.21
	(b) Wei, W.; Liu, X.; Yang, D.; Dong, R.; Cui, Y.; Yuan, F.; Wang, H. Tetrahedron Lett. 2015, 56,1808. doi: 10.1016/j.tetlet.2015.02.043
	(c) Hu, F.; Gao, W.; Chang, H.; Li, X.; Wei, W. Chin. J. Org. Chem. 2015, 35, 1848. (in Chinese) doi: 10.6023/cjoc201504039
	(胡飞, 高文超, 常宏宏, 李兴, 魏文珑, 有机化学, 2015, 35, 1848.) doi: 10.6023/cjoc201504039
	(d) Chen, F.; Zhou, N.; Zhan, J.; Han, B.; Yu, W. Org. Chem. Front. 2017, 4, 135. doi: 10.1039/C6QO00535G
[23]	Terent'ev, A.; Mulina, O.; Pirgach, D.; Nikishin, G. Tetrahedron Lett. 2017, 73, 6871. doi: 10.1016/j.tet.2017.10.047
[24]	Yuan, Y.; Cao, Y.; Lin, Y.; Li, Y.; Huang, Z.; Lei, A. ACS Catal. 2018, 8, 10871. doi: 10.1021/acscatal.8b03302
[25]	Mulina, O.; Ilovaisky, A.; Opatz, T.; Terent’ev, A. Tetrahedron Lett. 2021, 64, 152737. doi: 10.1016/j.tetlet.2020.152737
[26]	(a) Tan, C.; Liu, Y.; Liu, H.; Xu, K.; Huang, S.; Wang, J.; Tan, J. Org. Chem. Front. 2020, 7, 780. doi: 10.1039/C9QO01489F
	(b) Yan, Y.; Xu, Y.; Niu, B.; Xie, H.; Liu, Y. J. Org. Chem. 2015, 80, 5581. doi: 10.1021/acs.joc.5b00474
	(c) Fan, W.; Yang, Z.; Jiang, B.; Li, G. Org. Chem. Front. 2017, 4, 1091. doi: 10.1039/C6QO00851H
[27]	Tang, X.; Huang, L.; Xu, Y.; Yang, J.; Wu, W.; Jiang, H. Angew. Chem. 2014, 126, 4289. doi: 10.1002/ange.201311217
[28]	Sun, X.; Lyu, Y.; Zhang-Negrerie, D.; Du, Y.; Zhao, K. Org. Lett. 2013, 15, 6222. doi: 10.1021/ol4030716
[29]	Gao, P.; Wang, J.; Bai, Z.; Shen, L.; Yan, Y.; Yang, D.; Fan, M.; Guan, Z. Org. Lett. 2016, 18, 6074. doi: 10.1021/acs.orglett.6b03060
[30]	Bohnen, C.; Bolm, C. Org. Lett. 2015, 17, 3011. doi: 10.1021/acs.orglett.5b01384
[31]	Tang, X.; Huang, L.; Xu, Y.; Yang, J.; Wu, W.; Jiang, H. Angew. Chem., nt. Ed. 2014, 53, 4205.
[32]	Ning, Y.; Zhao, X.; Wu, Y.; Bi, X. Org. Lett. 2017, 19, 6240. doi: 10.1021/acs.orglett.7b03204
[33]	(a) Gang, F.; Xu, G.; Dong, T.; Yang, L.; Du, Z. Chin. J. Org. Chem. 2015, 35, 1428. (in Chinese) doi: 10.6023/cjoc201502020
	(刚芳莉, 徐光利, 董涛生, 杨丽, 杜正银, 有机化学, 2015, 35, 1428.) doi: 10.6023/cjoc201502020
	(b) Xu, G.; Gang, F.; Dong, T.; Fu, Y.; Du, Z. Chin. J. Org. Chem. 2016, 36, 1513. (in Chinese) doi: 10.6023/cjoc201601028
	(徐光利, 刚芳莉, 董涛生, 傅颖, 杜正银, 有机化学, 2016, 36, 1513.) doi: 10.6023/cjoc201601028
	(c) Wu, H.; Wu, J.; Du, Z. Chin. J. Org. Chem. 2017, 37, 1127. (in Chinese) doi: 10.6023/cjoc201610034
	(吴慧, 武俊成, 杜正银, 有机化学, 2017, 37, 1127.) doi: 10.6023/cjoc201610034
	(d) Zhang, W.; Dong, T.; Wang, T.; Du, Z. J. Liaocheng Univ. (Nat. Sci.) 2019, 32, 35. (in Chinese)
	(张文莹, 董涛生, 王天昀, 杜正银, 聊城大学学报(自然科学版), 2019, 32, 35.)
	(e) Hu, B.; Zhang, Y.; Wang, T.; Du, Z. J. Liaocheng Univ. (Nat. Sci.) 2020, 33, 67. (in Chinese)
	(胡贝, 张源民, 王天昀, 杜正银, 聊城大学学报(自然科学版), 2020, 33, 67.)
	(f) Li, H.; Yang, P.; Xu, Z.; Du, Z.; Fu, Y. Chin. J. Org. Chem. 2020, 40, 2476. (in Chinese) doi: 10.6023/cjoc202002042
	(李怀贵, 杨澎, 许峥, 杜正银, 傅颖, 有机化学, 2020, 40, 2476.) doi: 10.6023/cjoc202002042
[34]	Pan, X.; Gao, J.; Liu, J.; Lai, J.; Jiang, H.; Yuan, G. Green Chem. 2015, 17, 1400. doi: 10.1039/C4GC02115K
[35]	Wang, Y.; HervLonca, G.; Chiba, S. Angew. Chem., Int. Ed. 2014, 53, 1067. doi: 10.1002/anie.201307846
[36]	Mulina, O.; Zhironkina, N.; Paveliev, S.; Demchuk, D.; Terent'ev, A. Org. Lett. 2020, 22, 1818. doi: 10.1021/acs.orglett.0c00139 pmid: 32077294
[37]	Liu, Q.; Zhang, J.; Zhao, G.; Lei, A. J. Am. Chem. Soc. 2013, 135, 11481. doi: 10.1021/ja4052685
[38]	Yi, D.; He, L.; Qi, Z.; Zhang, Z.; Li, M.; Fu, Q.; Wei, S. Chin. J. Chem. 2021, 39, 859. doi: 10.1002/cjoc.v39.4