BF3•OEt2 Mediated Intramolecular Cyclization of 2-Alkynylanilines Approach to 3-Sulfenylindoles

doi:10.6023/cjoc202403041

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (9): 2785-2795.DOI: 10.6023/cjoc202403041 Previous Articles Next Articles

ARTICLES

BF₃•OEt₂介导2-炔基苯胺的分子内环化反应合成3-硫醚吲哚化合物

高宇珅^a^,^b, 高媛媛^b, 张安安^b, 李路^b, 耿巍芝^c, 张凤华^a^,^*(), 李飞^a^,^*(), 刘澜涛^a^,^b^,^*()

a 辽宁石油化工大学石油化工学院辽宁抚顺 113001
b 商丘师范学院化学化工学院河南省药物绿色合成工程研究中心河南商丘 476000
c 新乡润宇材料有限公司河南新乡 453000

收稿日期:2024-03-26 修回日期:2024-05-08 发布日期:2024-05-30
通讯作者: 张凤华, 李飞, 刘澜涛
基金资助:
河南省自然科学基金(232300421234); 河南省高校重点科研项目(24B150027); 河南省高校重点科研项目(24A530007); 商丘市科技创新领军人才(SQRC202212004); 商丘师范学院(黄河故道区生态环境保护计划)

BF₃•OEt₂ Mediated Intramolecular Cyclization of 2-Alkynylanilines Approach to 3-Sulfenylindoles

Yushen Gao^a^,^b, Yuanyuan Gao^b, An'an Zhang^b, Lu Li^b, Weizhi Geng^c, Fenghua Zhang^a(), Fei Li^a(), Lantao Liu^a^,^b()

a School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun, Liaoning 113001
b Henan Engineering Research Center of Green Synthesis for Pharmaceuticals, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000
c Xinxiang Runyu Material Co. Ltd., Xinxiang, Henan 453000

Received:2024-03-26 Revised:2024-05-08 Published:2024-05-30
Contact: Fenghua Zhang, Fei Li, Lantao Liu
Supported by:
Natural Science Foundation of Henan Province(232300421234); Key Scientific Research Project of Colleges and Universities in Henan Province(24B150027); Key Scientific Research Project of Colleges and Universities in Henan Province(24A530007); Leading Talents in Scientific and Technological Innovation in Shangqiu City(SQRC202212004); Shangqiu Normal University(Program of Ecological Environmental Protection in the Area of Old Course of Yellow River)

1. .pdf(5105KB)

Abstract

3-Sulfenylindoles are widely found in natural products, bioactive molecules and organic functional materials. BF₃•OEt₂ mediated electrophilic cyclization reaction of 2-alkynylaniline with N-(arylthio)succinimide was developed leading to the efficient synthesis of various biologically active 3-sulfenylindoles in moderate to high yields under very mild conditions. This protocol has the advantages of broad scope, functional group diversity, mild conditions and ease of operation. Moreover, gram-scale preparation portends the practical application.

Key words: 2-alkynylaniline, electrophilic cyclization, metal-free catalysis, 3-sulfenylindole

Cite this article

Yushen Gao, Yuanyuan Gao, An'an Zhang, Lu Li, Weizhi Geng, Fenghua Zhang, Fei Li, Lantao Liu. BF₃•OEt₂ Mediated Intramolecular Cyclization of 2-Alkynylanilines Approach to 3-Sulfenylindoles[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2785-2795.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 8

References 23

[1]	(a) Bingul, M.; Ercan, S.; Boga, M. J. Mol. Struct. 2020, 1213, 10. pmid: 17254785
	(b) Sarva, S.; Harinath, J. S.; Sthanikam, S. P.; Ethiraj, S.; Vaithiyalingam, M.; Cirandur, S. R. Chin. Chem. Lett. 2016, 27, 16. pmid: 17254785
	(c) Tu, M. S.; Chen, K. W.; Wu, P.; Zhang, Y. C.; Liu, X. Q.; Shi, F. Org. Chem. Front. 2021, 8, 2643. pmid: 17254785
	(d) Yamamoto, Y.; Kurazono, M. Bioorg. Med. Chem. Lett. 2007, 17, 1626. pmid: 17254785
	(e) Zhang, M. Z.; Chen, Q.; Yang, G. F. Eur. J. Med. Chem. 2015, 89, 421. pmid: 17254785
	(f) Zhang, M. Z.; Jia, C. Y.; Gu, Y. C.; Mulholland, N.; Turner, S.; Beattie, D.; Zhang, W. H.; Yang, G. F.; Gough, J. Eur. J. Med. Chem. 2017, 126, 669. pmid: 17254785
[2]	(a) Ragno, R.; Artico, M.; De Martino, G.; La Regina, G.; Coluccia, A.; Di Pasquali, A.; Silvestri, R. J. Med. Chem. 2005, 48, 213. pmid: 12773052
	(b) Ragno, R.; Coluccia, A.; La Regina, G.; De Martino, G.; Piscitelli, F.; Lavecchia, A.; Novellino, E.; Bergamini, A.; Ciaprini, C.; Sinistro, A.; Maga, G.; Crespan, E.; Artico, M.; Silvestri, R. J. Med. Chem. 2006, 49, 3172. pmid: 12773052
	(c) Silvestri, R.; Artico, M.; De Martino, G. L.; La Regina, G.; Loddo, R.; La Colla, M.; La Colla, P. J. Med. Chem. 2004, 47, 3892. pmid: 12773052
	(d) Silvestri, R.; De Martino, G.; La Regina, G.; Artico, M.; Massa, S.; Vargiu, L.; Mura, M.; Loi, A. G.; Marceddu, T.; La Colla, P. J. Med. Chem. 2003, 46, 2482. pmid: 12773052
[3]	Hutchinson, J. H.; Riendeau, D.; Brideau, C.; Chan, C.; Delorme, D.; Denis, D.; Falgueyret, J. P.; Fortin, R.; Guay, J.; Hamel, P.; Jones, T. R.; Macdonald, D.; McFarlane, C. S.; Piechuta, H.; Scheigetz, J.; Tagari, P.; Therien, M.; Girard, Y. J. Med. Chem. 1993, 36, 2771. pmid: 8410991
[4]	Hu, C. Y.; Ma, S. T. MedChemComm 2018, 9, 212.
[5]	(a) La Regina, G.; Edler, M. C.; Brancale, A.; Kandil, S.; Coluccia, A.; Piscitelli, F.; Hamel, E.; De Martino, G.; Matesanz, R.; Díaz, J. F.; Scovassi, A. I.; Prosperi, E.; Lavecchia, A.; Novellino, E.; Artico, M.; Silvestri, R. J. Med. Chem. 2007, 50, 2865.
	(b) Wan, Y. C.; Li, Y. H.; Yan, C. X.; Yan, M.; Tang, Z. L. Eur. J. Med. Chem. 2019, 183, 18.
[6]	(a) Benchawan, T.; Maneewong, J.; Saeeng, R. ChemistrySelect 2023, 8, e202301988.
	(b) Ge, X.; Sun, F. L.; Liu, X. M.; Chen, X. Z.; Qian, C.; Zhou, S. D. New J. Chem. 2017, 41, 13175.
	(c) Li, J.; Li, C.; Yang, S.; An, Y.; Wu, W.; Jiang, H. J. Org. Chem. 2016, 81, 7771.
	(d) Maeda, Y.; Koyabu, M.; Nishimura, T.; Uemura, S. J. Org. Chem. 2004, 69, 7688.
	(e) Yadav, J. S.; Reddy, B. V. S.; Reddy, Y. J.; Praneeth, K. Synthesis 2009, 2009, 1520.
	(f) Silveira, C. C.; Mendes, S. R.; Wolf, L.; Martins, G. M. Tetrahedron Lett. 2010, 51, 2014.
[7]	(a) Bai, F.; Zhang, S.; Wei, L.; Liu, Y. Asian J. Org. Chem. 2018, 7, 371. pmid: 29243330
	(b) Chen, M.; Huang, Z.-T.; Zheng, Q.-Y. Chem. Commun. 2012, 48, 11686. pmid: 29243330
	(c) Chen, M.; Luo, Y.; Zhang, C.; Guo, L.; Wang, Q.; Wu, Y. Org. Chem. Front. 2019, 6, 116. doi: 10.1039/c8qo00726h pmid: 29243330
	(d) Guo, W.; Tan, W.; Zhao, M. M.; Tao, K. L.; Zheng, L. Y.; Wu, Y. Q.; Chen, D. L.; Fan, X. L. RSC Adv. 2017, 7, 37739. pmid: 29243330
	(e) He, X.; Song, W.; Liu, X.; Huang, J.; Feng, R.; Zhou, S.; Hong, J.; Ge, X. Green Chem. 2023, 25, 1311. pmid: 29243330
	(f) Li, W. H.; Wang, H.; Liu, S. P.; Feng, H.; Benassi, E.; Qian, B. Adv. Synth. Catal. 2020, 362, 2666. pmid: 29243330
	(g) Liu, H. L.; Zhang, R. J.; Han, D. Y.; Feng, Y.; Luo, T. H.; Xu, D. Z. J. Org. Chem. 2023, 88, 10058. doi: 10.1021/acs.joc.3c00906 pmid: 29243330
	(h) Menezes, J. R.; Gularte, M. M.; dos Santos, F. C.; Roehrs, J. A.; Azeredo, J. B. Tetrahedron Lett. 2023, 120, 154446. pmid: 29243330
	(i) Mulina, O. M.; Ilovaisky, A. I.; Terent'ev, A. O. ChemistrySelect 2021, 6, 10369. doi: 10.1002/slct.202102227 pmid: 29243330
	(j) Nandi, G. C.; Priya, V. R. P.; Mercy, A. A. H.; Natarajan, K. Synlett 2023, 34, 279. pmid: 29243330
	(k) Pandey, A. K.; Chand, S.; Singh, R.; Kumar, S.; Singh, K. N. ACS Omega 2020, 5, 7627. doi: 10.1021/acsomega.0c00472 pmid: 29243330
	(l) Qi, H.; Zhang, T.; Wan, K.; Luo, M. J. Org. Chem. 2016, 81, 4262. pmid: 29243330
	(m) Rafique, J.; Saba, S.; Franco, M. S.; Bettanin, L.; Schneider, A. R.; Silva, L. T.; Braga, A. L. Chem.-Eur. J. 2018, 24, 4173. doi: 10.1002/chem.201705404 pmid: 29243330
	(n) Raghuvanshi, D. S.; Verma, N. RSC Adv. 2017, 7, 22860. pmid: 29243330
	(o) Rastogi, S. K.; Singh, R.; Kumar, S.; Mishra, A. K.; Ahirwar, M. B.; Deshmukh, M. M.; Sinha, A. K.; Kumar, R. Org. Biomol. Chem. 2023, 21, 838. pmid: 29243330
	(p) Shen, Z.; Li, M.; Xu, C.; Yi, S.; Hu, X.; Sun, N.; Jin, L.; Hu, B. Synlett 2018, 29, 1914. pmid: 29243330
	(q) Sorabad, G. S.; Maddani, M. R. Asian J. Org. Chem. 2019, 8, 1336. pmid: 29243330
	(r) Sun, S. N.; Ye, H. X.; Liu, H. B.; Guo, Y. B.; Gao, Z. H.; Pan, L.; Li, J. C.; Bi, X. J. ChemistryOpen 2023, 12, e202300002. pmid: 29243330
	(s) Thurow, S.; Penteado, F.; Perin, G.; Alves, D.; Santi, C.; Monti, B.; Schiesser, C. H.; Barcellos, T.; Lenardão, E. J. Org. Chem. Front. 2018, 5, 1983. pmid: 29243330
	(t) Truong, T. S.; Retailleau, P.; Nguyen, T. B. Asian J. Org. Chem. 2022, 11, e202100751. pmid: 29243330
	(u) Tudge, M.; Tamiya, M.; Savarin, C.; Humphrey, G. R. Org. Lett. 2006, 8, 565. pmid: 29243330
[8]	((a) Xu, X.; Li, J.; Wang, Z. Chin. J. Org. Chem. 2020, 40, 886 (in Chinese).
	(徐鑫明, 李家柱, 王祖利, 有机化学, 2020, 40, 886.) doi: 10.6023/cjoc201910020
	(b) Tong, Y.; Wang, Z.; Liu, B.; Xu, Y.; Gao, S.; Tang, X.; Zhang, X. Chin. J. Org. Chem. 2023, 43, 1310 (in Chinese).
	(童宇星, 王子维, 刘奔, 徐耀威, 高颂, 唐向兵, 张兴华, 有机化学, 2023, 43, 1310.) doi: 10.6023/cjoc202211012
[9]	(a) Humphrey, G. R.; Kuethe, J. T. Chem. Rev. 2006, 106, 2875. pmid: 21779596
	(b) Barluenga, J.; Rodríguez, F.; Fañanás, F. J. Chem.-Asian J. 2009, 4, 1036. pmid: 21779596
	(c) Vicente, R. Org. Biomol. Chem. 2011, 9, 6469. doi: 10.1039/c1ob05750b pmid: 21779596
	(d) Ayesha; Bilal, M.; Rasool, N.; Khan, S. G.; Rashid, U.; Altaf, H.; Ali, I. Catalysts 2021, 11, 1018. pmid: 21779596
	(e) Krüger, K.; Tillack, A.; Beller, M. Adv. Synth. Catal. 2008, 350, 2153. pmid: 21779596
	(f) Cacchi, S.; Fabrizi, G. Chem. Rev. 2005, 105, 2873. pmid: 21779596
[10]	Guo, Y. J.; Tang, R. Y.; Li, J. H.; Zhong, P.; Zhang, X. G. Adv. Synth. Catal. 2009, 351, 2615.
[11]	Li, J. X.; Li, C. S.; Yang, S. R.; An, Y. N.; Wu, W. Q.; Jiang, H. F. J. Org. Chem. 2016, 81, 2875.
[12]	Li, J. X.; Tang, H.; Lin, Z. D.; Yang, S. R.; Wu, W. Q.; Jiang, H. F. Org. Biomol. Chem. 2020, 18, 4071.
[13]	Chen, Y.; Cho, C. H.; Larock, R. C. Org. Lett. 2009, 11, 173. doi: 10.1021/ol8021287 pmid: 19046068
[14]	Du, H. A.; Tang, R. Y.; Deng, C. L.; Liu, Y.; Li, J. H.; Zhang, X. G. Adv. Synth. Catal. 2011, 353, 2739.
[15]	Chen, W. C.; Bai, R. K.; Cheng, W. L.; Peng, C. Y.; Reddy, D. M.; Badsara, S. S.; Lee, C. F. Org. Biomol. Chem. 2023, 21, 3002.
[16]	(a) Han, D. D.; Li, Z. M.; Fan, R. H. Org. Lett. 2014, 16, 6508.
	(b) Li, X. M.; Zhang, B. B.; Zhang, J. R.; Wang, X.; Zhang, D. K.; Du, Y. F.; Zhao, K. Chin. J. Chem. 2021, 39, 1211.
	(c) Li, X. M.; Sun, F. X.; Shi, H. F.; Zhang, B. B.; He, J. X.; Wu, J. L.; Du, Y. F. Org. Lett. 2023, 25, 3517.
[17]	(a) Cao, R. F.; Yu, L.; Huo, Y. X.; Li, Y.; Xue, X. S.; Chen, Z. M. Org. Lett. 2022, 24, 4093. pmid: 31525984
	(b) Wei, W.; Liao, L. H.; Qin, T.; Zhao, X. D. Org. Lett. 2019, 21, 7846. doi: 10.1021/acs.orglett.9b02834 pmid: 31525984
[18]	He, Y. P.; Wu, H.; Wang, Q.; Zhu, J. P. Angew. Chem., Int. Ed. 2020, 59, 2105.
[19]	Hostier, T.; Ferey, V.; Ricci, G.; Pardo, D. G.; Cossy, J. Org. Lett. 2015, 17, 3898. doi: 10.1021/acs.orglett.5b01889 pmid: 26205587
[20]	Inamoto, K.; Asano, N.; Nakamura, Y.; Yonemoto, M.; Kondo, Y. Org. Lett. 2012, 14, 2622.
[21]	Yang, W. C.; Chen, X. B.; Song, K. L.; Wu, B.; Gan, W. E.; Zheng, Z. J.; Cao, J.; Xu, L. W. Org. Lett. 2021, 23, 1309.
[22]	Kesavan, A.; Anbarasan, P. Chem. Commun. 2022, 58, 282.
[23]	Annese, C.; D'Accolti, L.; Fusco, C.; Licini, G.; Zonta, C. Chem.-Eur. J. 2017, 23, 259.

Entry	BF₃•OEt₂/mol%	Dosage/equiv. of 1a/2a	T/℃	Solvent	Yield^b/%
1	10	1/1.2	30	DCM	35
2	20	1/1.2	30	DCM	78
3	30	1/1.2	30	DCM	89
4	20	1/1.5	30	DCM	98
5	20	1/1.5	30	Toluene	17
6	20	1/1.5	30	THF	Trace
7	20	1/1.5	30	CH₃CN	Trace
8	20	1/1.5	30	DCE	98
9^c	20	1/1.5	40	DCE	99
10^d	20	1/1.5	50	DCE	99

Entry	BF₃•OEt₂/mol%	Dosage/equiv. of 1a/2a	T/℃	Solvent	Yield^b/%
1	10	1/1.2	30	DCM	35
2	20	1/1.2	30	DCM	78
3	30	1/1.2	30	DCM	89
4	20	1/1.5	30	DCM	98
5	20	1/1.5	30	Toluene	17
6	20	1/1.5	30	THF	Trace
7	20	1/1.5	30	CH₃CN	Trace
8	20	1/1.5	30	DCE	98
9^c	20	1/1.5	40	DCE	99
10^d	20	1/1.5	50	DCE	99

BF₃•OEt₂介导2-炔基苯胺的分子内环化反应合成3-硫醚吲哚化合物

BF₃•OEt₂ Mediated Intramolecular Cyclization of 2-Alkynylanilines Approach to 3-Sulfenylindoles

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 8

References 23

Related Articles 10

Recommended Articles

Metrics

Comments

[1]	Yunhui Wan, Fumei Yang, Minghan Chen, Deli Sun, Danfeng Ye. Esterification of N-Benzyl-N-t-butoxycarbonyl-amides and Unsaturated Alcohol under Transition Metal-Free Conditions [J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1293-1300.
[2]	Biao Ma, Miaomiao Zhang, Zhanyu Li, Jinsong Peng, Chunxia Chen. Recent Advance of Transition Metal-Free Catalyzed Suzuki-Type Cross Coupling Reaction [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 455-470.
[3]	Zhixin Zhang, Tongyi Zhai, Bohan Zhu, Pengcheng Qian, Longwu Ye. Synthesis of Tetrahydroindole Derivatives via Metal-Free Intramolecular [4+2] Annulation of Ynamides [J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1501-1508.
[4]	Renhong Chen, Guizhen Wu, Kai Yang, Bin Ye, Qingfeng Chen, Zhaoyang Wang. One-Pot Synthesis ofN-Furanonyl Sulfonyl Hydrazone Compounds [J]. Chinese Journal of Organic Chemistry, 2021, 41(7): 2750-2759.
[5]	Kunchen Xie, Mingxuan Jiang, Xiaolan Chen, Qiyan Lü, Bing Yu. Application of α-Keto Acids in Metal-Free Photocatalysis [J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4575-4587.
[6]	Li Mingrui, Ding Qifeng, Li Boyang, Yu Yang, Huang He, Huang Fei. Progress in the Synthesis of 1,2,4-Triazines by Tandem Cyclization [J]. Chinese Journal of Organic Chemistry, 2019, 39(10): 2713-2725.
[7]	Zhang Zhenbei, Sun Wei, Cao Zhishan. Progress in Activation of Small Molecules Promoted by Frustrated Lewis Pairs [J]. Chin. J. Org. Chem., 2018, 38(6): 1292-1318.
[8]	Hu Fei, Gao Wenchao, Chang Honghong, Li Xing, Wei Wenlong. Progress in Iodine-Mediated Sulfonylation Reactions [J]. Chin. J. Org. Chem., 2015, 35(9): 1848-1860.
[9]	Chen Jing, Qu Hongmei, Peng Jing, Chen Chao. Study of Electrophilic Cyclization Reactions Triggered by Diaryliodonium Salts [J]. Chin. J. Org. Chem., 2015, 35(5): 937-946.
[10]	Luo Qian, Xie Yongxin, Chen Zhaoyang, Yan Shiyou, Deng Wenye, Liu Yi, Wang Lulu. Synthesis of Bis(iodo-benzopyran) Derivatives and Bis(iodo-2H-quinoline) Derivatives by Electrophilic Cyclization [J]. Chin. J. Org. Chem., 2014, 34(12): 2537-2542.

BF3•OEt2介导2-炔基苯胺的分子内环化反应合成3-硫醚吲哚化合物