A Mild and Efficient Catalytic Aerobic Oxidative Dehydrogenation of N-Pyridylindolines

doi:10.6023/cjoc202009054

Abstract

An efficient and mild N-hydroxyphthalimide and copper co-catalyzed aerobic oxidative dehydrogenation of N-pyridylindolines is developed. The use of air as sole oxidant allows a green, safe, low-cost and simple operation. This method provides an alternative to the known method for the oxidation of N-pyridylindoline derivatives by the use of excess stoichiometric strong oxidant 2,3-dichloro-5,6-dicyanobenzoquinone.

Key words: N-hydroxyphthalimide, dehydrogenation, N-pyridylindolines, air condition, oxidation reaction

Cite this article

Hao Tang, Beibei Zhang, Weidong Chen, Junfei Luo. A Mild and Efficient Catalytic Aerobic Oxidative Dehydrogenation of N-Pyridylindolines[J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1131-1137.

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Fig. & Tab. 7

Scheme 1. Transformations of indolines to indoles

Entry	Cu(OAc)₂?H₂O/ mol%	NHPI/ mol%	Solvent	Yield/%
1	5	20	MeCN	94
2	5	20	Toluene	60
3	5	20	1,4-Dioxane	61
4	5	20	THF	40
5	5	20	DMF	0
6	5	40	MeCN	85
7	5	—	MeCN	0
8	—	20	MeCN	30
9^b	5	20	MeCN	93
10^c	5	20	MeCN	Trace
11^d	—	20	MeCN	6

Table 1. Optimization of reaction conditionsa

Table 2. Scope of N-pyridylindolines oxidationa

Scheme 2. Scale-up reaction.

Scheme 3. Oxidation of C(7)-decorated indolines

Scheme 4. Control reactions

Scheme 5. Proposed reaction mechanism

References 27

[1]	(a) Bariwal, J.; Voskressensky, L. G.; Van der Eycken, E. V. Chem. Soc. Rev. 2018, 47, 3831. pmid: 29632917
	(b) Xie, T.-Z.; Zhao, Y.-L.; Ma, W.-G.; Wang, Y.-F.; Yu, H.-F.; Wang, B.; Wei, X.; Huang, Z.-P.; Zhu, P.-F.; Liu, Y.-P.; Luo, X.-D. Chin. J. Org. Chem. 2020, 40, 679. (in Chinese) pmid: 29632917
	(解天珍, 赵云丽, 马伟光, 王易芬, 于浩飞, 王蓓, 魏鑫, 黄之镨, 朱培凤, 刘亚平, 罗晓东, 有机化学, 2020, 40, 679.) pmid: 29632917
	(c) Huang, J.; Luo, S.; Gong, L. Acta Chim. Sinica 2013, 71, 879. (in Chinese) doi: 10.6023/A13020217 pmid: 29632917
	(黄建洲, 罗时玮, 龚流柱, 化学学报, 2013, 71, 879.) pmid: 29632917
	(d) America, M.; Asgharia, A.; Amoozadeha, A.; Bakherad, M.; Chin. Chem. Lett. 2017, 28, 1031. pmid: 29632917
	(e) Liang, K. J.; Xia, C. F. Chin. J. Chem. 2017, 35, 255. pmid: 29632917
[2]	(a) Bandini, M.; Eichholzer, A. Angew. Chem.. Int. Ed. 2009, 48, 9608. pmid: 19777071
	(b) Barluenga, J.; Rodriguez, F.; Fananas, F. J. Chem.-Asian J. 2009, 4, 1036. pmid: 19777071
	(c) Shi, Z.; Zhang, C.; Li, S.; Pan, D.; Ding, S.; Cui, Y.; Jiao, N. Angew. Chem.. Int. Ed. 2009, 48, 4572. pmid: 19777071
	(d) Taber, D. F.; Tirunahari, P. K. Tetrahedron 2011, 67, 7195. doi: 10.1016/j.tet.2011.06.040 pmid: 19777071
	(e) Shi, Z.; Nie, K.; Liu, C.; Zhang, M.; Zhang, W. Chin. J. Org. Chem. 2020, 40, 327. (in Chinese) pmid: 19777071
	(施展, 聂克睿, 刘畅, 张明智, 章维华, 有机化学, 2020, 40, 327.) pmid: 19777071
	(f) Yu, K.; Gao, B.; Ding, H. Acta Chim. Sinica 2016, 74, 410. (in Chinese) pmid: 19777071
	(余宽, 高北岭, 丁寒锋, 化学学报, 2016, 74, 410.) a94c3463-b409-4364-8925-1fbcb8fbd4c0 doi: 10.6023/A16020102 pmid: 19777071
	(g) Huang, E.; Zhang, L., Xiao, C.; Meng, G.; Zhang, B.; Hu, J.; Wan, D. C.-C.; Meng, Q.; Jin, Z.; Hua, C. Chin. Chem. Lett., 2019, 30, 2157. pmid: 19777071
	(h) Cerveri, A.; Bandini, M. Chin. J. Chem. 2020, 38, 287. doi: 10.1002/cjoc.v38.3 pmid: 19777071
	(i) Yang, P.; Xu, R.-Q.; Zheng, C.; You, S.-L. Chin. J. Chem. 2020, 38, 235. pmid: 19777071
[3]	(a) Thikekar, T. U.; Selvaraju, M.; Sun, C.-M. Org. Lett. 2016, 18, 316. pmid: 27700080
	(b) Peng, F.; McLaughlin, M.; Liu, Y.; Mangion, I.; Tschaen, D. M.; Xu, Y. J. Org. Chem. 2016, 81, 10009. doi: 10.1021/acs.joc.6b01854 pmid: 27700080
	(c) Zhang, J.; Chen, S.; Chen, F.; Xu, W.; Deng, G.-J.; Gong, H. Adv. Synth. Catal. 2017, 359, 2358. pmid: 27700080
	(d) Huo, H.-R.; Tang, X.-Y.; Gong, Y.-F. Synthesis 2018, 50, 2727. pmid: 27700080
	(e) Taboonpong, P.; Chavasiri, W. Catal. Commun. 2018, 104, 9. doi: 10.1016/j.catcom.2017.10.009 pmid: 27700080
	(f) Zhu, R.; Zhai, M.; Liu, S.; Liu, X.; Wang, Z.; Ju, R.; Yu, X. Chin. J. Org. Chem. 2020, 40, 2045. (in Chinese) pmid: 27700080
	(朱润宇, 翟民, 刘霜, 刘星彤, 王振, 居瑞军, 虞心红, 有机化学, 2020, 40, 2045.) pmid: 27700080
[4]	(a) Pratt, E. F.; McGovern, T. P. J. Org. Chem. 1964, 29, 1540.
	(b) Kawase, M.; Miyake, Y.; Kikugawa, Y. J. Chem. Soc.. Perkin Trans. 1 1984,1401.
	(c) Giethlen, B.; Schaus, J. M. Tetrahedron Lett. 1997, 38, 8483. doi: 10.1016/S0040-4039(97)10306-9
	(d) Mukaiyama, T.; Kawana, A.; Fukuda, Y.; Matsuo, J. Chem. Lett. 2001,390.
	(e) Tilstam, Kawana, U.; Harre, M.; Heckrodt, T.; Weinmann, H. Tetrahedron Lett. 2001, 42, 5385.
[5]	(a) Zhang, X.; Liu, W.; Sun, D.; Huang, J.; Qiu, X.; Li, Z.; Wu, Z. ChemSusChem 2020,4774. pmid: 25330125
	(b) Chen, H.; Liu, L.; Huang, T.; Chen, J.; Chen, T. Adv. Synth. Catal. 2020,3332. pmid: 25330125
	(c) Tang, H.; Luo, J.; Xie, P. Chin. J. Org. Chem. 2019, 39, 2735. (in Chinese) pmid: 25330125
	(唐灏, 骆钧飞, 解攀, 有机化学, 2019, 39, 2735.) pmid: 25330125
	(d) Zhang, Z.; Tian, Q.; Qian, J.; Liu, Q.; Liu, T.; Shi, L.; Zhang, G. J. Org. Chem. 2014, 79, 8182. pmid: 25330125
	(e) Qian, J.; Zhang, Z.; Liu, Q.; Liu, T.; Zhang, G. Adv. Synth. Catal. 2014, 356, 3119. pmid: 25330125
	(f) Zhang, Z.; Zhang, W.; Li, J.; Liu, Q.; Liu, T.; Zhang, G. J. Org. Chem. 2014, 79, 11226. pmid: 25330125
[6]	(a) Wang, Q.; Chai, H.; Yu, Z. Organometallics 2018, 37, 584.
	(b) He, K. H.; Tan, F. F.; Zhou, C. Z.; Zhou, G.-J.; Yang, X.-L.; Li, Y. Angew. Chem.. Int. Ed. 2017, 56, 3080.
[7]	(a) Lou, C.; Qin, S.; Zhang, S.; Lv, Z.; Senan, A.; Chen, Z.; Yin, G. Catal. Commun. 2017, 90, 5.
	(b) Hara, T.; Mori, K.; Mizugaki, T.; Ebitani, K.; Kaneda, K. Tetrahedron Lett. 2003, 44, 6207.
[8]	(a) Elumalai, K.; Weng, K. L. Tetrahedron Lett. 2018, 59, 3958. pmid: 19777526
	(b) So, M. H.; Liu, Y.; Ho, C.-M.; Che, C.-M. Chem.-Asian J. 2009, 4, 1551. doi: 10.1002/asia.200900261 pmid: 19777526
[9]	(a) Zhou, W.; Chen, D.; Sun, F.; Qian, J.; He, M.; Chen, Q. Tetrahedron Lett. 2018, 59, 949. pmid: 26333043
	(b) Iosub, A. V.; Stahl, S. S. Org. Lett. 2015, 17, 4404. pmid: 26333043
[10]	(a) Jawale, D. V.; Gravel, E.; Shah, N.; Dauvois, V.; Li, H.; Namboothiri, I. N. N.; Doris, E. Chem.-Eur. J. 2015, 21, 7039. pmid: 24328193
	(b) Damodara, D.; Arundhathi, R.; Likhara, P. R. Adv. Synth. Catal. 2014, 356, 189. pmid: 24328193
	(c) Zhou, W.; Taboonpong, P.; Aboo, A. H.; Zhang, L.; Jiang, J.; Xiao, J. Synlett 2016, 27, 1806. pmid: 24328193
	(d) Cui, X.; Li, Y.; Bachmann, S.; Scalone, M.; Surkus, A.; Junge, K.; Topf, C.; Beller, M. J. Am. Chem. Soc. 2015, 137, 10652. pmid: 24328193
	(e) Wendlandt, A. E.; Stahl, S. S. J. Am. Chem. Soc. 2014, 136, 506. pmid: 24328193
	(f) Karki, M.; Araujo, H. C.; Magolan, J. Synlett 2013, 24, 1675. pmid: 24328193
[11]	(a) Kojima, M.; Kanai, M. Angew. Chem., Int. Ed. 2016, 55, 12224.
	(b) Maier, A. F. G.; Tussing, S.; Schneider, T.; Florke, U.; Qu, Z.-W.; Grimme, S.; Paradies, J. Angew. Chem.. Int. Ed. 2016, 55, 12219.
[12]	Chen, W.; Tang, H.; Wang, W.; Fu, Q.; Luo, J. Adv. Synth. Catal. 2020, 362, 3905.
[13]	(a) Burke, J. P.; Bian, Z.; Shaw, S.; Zhao, B.; Goodwin, C. M.; Belmar, J.; Browning, C. F.; Vigil, D.; Friberg, A.; Camper, D. V.; Rossanese, O. W.; Lee, T.; Olejniczak, E. T.; Fesik, S. W. J. Med. Chem. 2015, 58, 3794. doi: 10.1021/jm501984f pmid: 16854069
	(b) Ozawa, Y.; Kusano, K.; Owa, T.; Yokoi, A.; Asada, M.; Yoshimatsu, K. Cancer Chemother. Pharmacol. 2012, 69, 1353. doi: 10.1007/s00280-012-1844-8 pmid: 16854069
	(c) Dydio, P.; Zielinski, T.; Jurczak, J. Chem. Commun. 2009,4560. pmid: 16854069
	(d) Ferandin, Y.; Bettayeb, K.; Kritsanida, M.; Lozach, O.; Polychronopoulos, P.; Magiatis, P.; Skaltsounis, A.-L.; Meijer, L. J. Med. Chem. 2006, 49, 4638. doi: 10.1021/jm060314i pmid: 16854069
[14]	(a) Yang, X.-F.; Hu, X.-H.; Loh, T.-P. Org. Lett. 2015, 17, 1481. pmid: 23418946
	(b) Shin, Y.; Sharma, S.; Mishra, N. K.; Han, S.; Park, J.; Oh, H.; Ha, J.; Yoo, H.; Jung, Y. H.; Kim, I. S. Adv. Synth. Catal. 2015, 357, 594. doi: 10.1002/adsc.201400942 pmid: 23418946
	(c) Mishra, N. K.; Jeong, T.; Sharma, S.; Shin, Y.; Han, S.; Park, J.; Oh, J. S.; Kwak, J. H.; Jung, Y. H.; Kim, I. S. Adv. Synth. Catal. 2015, 357, 1293. pmid: 23418946
	(d) Xie, W.; Li, B.; Wang, B. J. Org. Chem. 2015, 81, 396. doi: 10.1021/acs.joc.5b01943 pmid: 23418946
	(e) Wang, X.; Tang, H.; Feng, H.; Li, Y.; Yang, Y.; Zhou, B. J. Org. Chem. 2015, 80, 6238. pmid: 23418946
	(f) Hou, W.; Yang, Y.; Ai, W.; Wu, Y.; Wang, X.; Zhou, B.; Li, Y. Eur. J. Org. Chem. 2015,395. pmid: 23418946
	(g) Park, J.; Mishra, N. K.; Sharma, S.; Han, S.; Shin, Y.; Jeong, T.; Oh, J. S.; Kwak, J. H.; Jung, Y. H.; Kim, I. S. J. Org. Chem. 2015, 80, 1818. pmid: 23418946
	(h) Yang, D.; Mao, S.; Gao, Y.-R.; Guo, D.-D.; Guo, S.-H.; Li, B.; Wang, Y.-Q. RSC Adv. 2015, 5, 23727. pmid: 23418946
	(i) Kim, M.; Mishra, N. K.; Park, J.; Han, S.; Shin, Y.; Sharma, S.; Lee, Y.; Lee, E.-K.; Kwak, J. H.; Kim, I. S. Chem. Commun. 2014, 50, 14249. pmid: 23418946
	(j) Pan, S.; Wakaki, T.; Ryu, N.; Shibata, T. Chem.-Asian J. 2014, 9, 1257. doi: 10.1002/asia.201301733 pmid: 23418946
	(k) Urones, B.; Arrayas, R. G.; Carretero, J. C. Org. Lett. 2013, 15, 1120. doi: 10.1021/ol400206k pmid: 23418946
[15]	(a) Ahmad, A.; Dutta, H. S.; Kumar, M.; Khan, A. A.; Raziullah, Koley, D. Org. Lett. 2020, 22, 5870. pmid: 25587810
	(b) Ahmad, A.; Dutta, H. S.; Khan, B.; Kant, R.; Koley, D. Adv. Synth. Catal. 2018, 360, 1644. doi: 10.1002/adsc.v360.8 pmid: 25587810
	(c) Zhai, W.; Li, B.; Wang, B. ChemistrySelect 2018, 3, 8035. pmid: 25587810
	(d) Ai, W.; Yang, X.; Wu, Y.; Wang, X.; Li, Y.; Yang, Y.; Zhou, B. Chem.-Eur. J. 2014, 20, 17653. pmid: 25587810
	(e) Wu, Y.; Yang, Y.; Zhou, B.; Li, Y. J. Org. Chem. 2015, 80, 1946. doi: 10.1021/jo502596k pmid: 25587810
[16]	Kumar, M.; Sharma, R.; Raziullah, Khan, A. A.; Ahmad, A.; Dutta, H. S.; Koley, D. Org. Lett. 2020, 22, 2152. pmid: 32129076
[17]	Gao, S.; Xu, X.; Tang, H.; Wu, J.-Q.; Luo, J. ChemistrySelect 2019, 4, 5835.
[18]	Zhi, C.; Wang, Q.; Liu, S.; Xue, Y.; Shi, L.; Zhu, X.; Hao, X.-Q.; Song, M.-P. J. Org. Chem. 2020, 85, 1022. pmid: 31833373
[19]	(a) Lee, J. M.; Park, E. J.; Cho, S. H.; Chang, S. J. Am. Chem. Soc. 2008, 130, 7824. doi: 10.1021/ja8031218 pmid: 28992686
	(b) Ishii, Y.; Sakaguchi, S.; Iwahamab, T. Adv. Synth. Catal. 2001, 343, 393. doi: 10.1002/(ISSN)1615-4169 pmid: 28992686
	(c) Bag, R.; Sar, D.; Punniyamurthy, T. Org. Lett. 2015, 17, 2010. pmid: 28992686
	(d) Zhou, W.-J.; Cao, G.-M.; Shen, G.; Zhu, X.-Y.; Gui, Y.-Y.; Ye, J.-H.; Sun, L.; Liao, L.-L.; Li, J.; Yu, D.-G. Angew. Chem.. Int. Ed. 2017, 56, 15683. doi: 10.1002/anie.201704513 pmid: 28992686
	(e) Parasram, M.; Chuentragool, P.; Wang, Y.; Shi, Y.; Gevorgyan, V. J. Am. Chem. Soc. 2017, 139, 14857. pmid: 28992686
[20]	Ackermann, L.; Lygin, A. V. Org. Lett. 2011, 13, 3332. doi: 10.1021/ol2010648 pmid: 21644545
[21]	Xu, S.; Huang, X.; Hong, X.; Xu, B. Org. Lett. 2012, 14, 4614. doi: 10.1021/ol302070t pmid: 22905784
[22]	Liang, L.; Fu, S.; Lin, D.; Zhang, X.-Q.; Deng, Y.; Jiang, H.; Zeng, W. J. Org. Chem. 2014, 79, 9472. pmid: 25251735
[23]	Li, T.; Wang, Z.; Zhang, M.; Zhang, H.-J.; Wen, T.-B. Chem. Commun. 2015, 51, 6777.
[24]	Liu, S.-L.; Li, Y.; Guo, J.-R.; Yang, G.-C.; Li, X.-H.; Gong, J.-F.; Song, M.-P. Org. Lett. 2017, 19, 4042. pmid: 28745899
[25]	Manna, M. K.; Bairy, G.; Jana, R. J. Org. Chem. 2018, 83, 8390. doi: 10.1021/acs.joc.8b01034 pmid: 29873230
[26]	Rull, S. G.; Blandez, J. F.; Fructos, M. R.; Belderrain, T. R.; Nicasio, M. C. Adv. Syn. Catal. 2015, 357, 907.
[27]	Gao, S.; Xu, X.; Tang, H.; Wu, J.-Q.; Luo, J. ChemistrySelect 2019, 4, 5835.

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