Copper-Catalyzed Aerobic Oxidation Strategy: A Concise Route to Isatin

doi:10.6023/cjoc201903024

Abstract

A copper-catalyzed decarbonylation cyclization to form isatins using oxygen as terminal oxidant is developed. This complementary way offers a new protocol for the synthesis of isatins through C(sp³)—H bond functionalization in Cu/O₂/Co system. This system shows good reactivity and compatibility. Both electron-rich and electron-deficient functional groups can be tolerated. A postulated mechanism is proposed based on mechanistic studies and previous reports.

Key words: Cu catalyst, C—H bond activation, isatin, decarbonylation, oxygen

Cite this article

Ahmad Muhammad Siddique, Zhu Yamin, Guo Yunlong, Zhang Saisai, Shen Zengming. Copper-Catalyzed Aerobic Oxidation Strategy: A Concise Route to Isatin[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3244-3249.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

References 20

[1]	(a) Sumpter, W. C. Chem. Rev. 1944, 34, 393. doi: 10.1021/cr60109a003
	(b) da Silva, J. F. M.; Garden, S. J.; Pinto, A. C. J. Braz. Chem. Soc. 2001, 12, 273. doi: 10.1021/cr60109a003
[2]	(a) Ratan, B. T.; Anand, B.; Yogeeswari, P.; Sriram, D. Bioorg. Med. Chem. Lett. 2005, 15, 4451. doi: 10.1016/j.bmcl.2005.07.046
	(b) Raj, A.; Raghunathan, R.; Sridevikumaria, M. R.; Raman, N. Bioorg. Med. Chem. 2003, 11, 407. doi: 10.1016/j.bmcl.2005.07.046
	(c) Verma, M.; Pandeya, S. N.; Singh, K. N.; Stables, J. P. Acta Pharm. 2004, 54, 49. doi: 10.1016/j.bmcl.2005.07.046
	(d) Jiang, T.; Kuhen, K. L.; Wolff, K.; Yin, H.; Bieza, K.; Caldwell, J.; Bursulaya, B.; Tuntlad, T.; Zhang, K.; Karanewsky, D.; He, Y. Bioorg. Med. Chem. Lett. 2006, 16, 2109. doi: 10.1016/j.bmcl.2005.07.046
	(e) Aboul-Fadl, T.; Bin-Jubair, F. A. S. Int. J. Res. Pharm. Sci. 2010, 1, 113. doi: 10.1016/j.bmcl.2005.07.046
	(f) Sharma, S.; Gupta, M. K.; Saxena, A. K.; Bedi, P. M. S. Bioorg. Med. Chem. 2015, 23, 7165. doi: 10.1016/j.bmcl.2005.07.046
	(g) Harbinder, S.; Jatinder, V. S.; Gupta, M. K.; Sharma, S.; Nepali, K.; Bedi, P. M. S. Bioorg. Med. Chem. Lett. 2017, 27, 3974. doi: 10.1016/j.bmcl.2005.07.046
[3]	Sandmeyer T. Helv. Chim. Acta 1919, 2 234. doi: 10.1002/hlca.19190020125
[4]	(a) Stollé, R. Ber. Dtsch. Chem. Ges. 1913, 46, 3915. doi: 10.1002/(ISSN)1099-0682
	(b) Stollé, R. J. Prakt. Chem. 1922, 106, 137. doi: 10.1002/(ISSN)1099-0682
[5]	(a) Martinet, J. Compt. Rend. 1918, 166, 85.
	(b) Bonnefoy, J.; Martinet, J. Compt. Rend. 1921, 172, 220.
[6]	Xie Y. Chem. Commun. 2016, 52 12372. doi: 10.1039/C6CC05769A
[7]	(a) Sun, J.; Liu, B.; Xu, B. RSC Adv. 2013, 3, 5824. doi: 10.1039/c3ra40657a
	(b) Liu, T.; Yang, H.; Jiang, Y.; Fu, H. Adv. Synth. Catal. 2013, 355, 1169. doi: 10.1039/c3ra40657a
	(c) Tang, B.-X.; Song, R.-J.; Wu, C.-Y.; Liu, Y.; Zhou, M.-B.; Wei, W.-T.; Deng, G.-B.; Yin, D.-L.; Li, J.-H. J. Am. Chem. Soc. 2010, 132, 8900. doi: 10.1039/c3ra40657a
	(d) Liu, T.; Yang, H.; Jiang, Y.; Fu, H. Adv. Synth. Catal. 2013, 355, 1169. doi: 10.1039/c3ra40657a
	(e) Sun, J.; Liu, B.-X.; Xu, B. RSC Adv. 2013, 3, 5824. doi: 10.1039/c3ra40657a
	(f) Ilangovan, A.; Satish, G. Org. Lett. 2013, 15, 5726. doi: 10.1039/c3ra40657a
	(g) Huang, P. C.; Gandeepan, P.; Cheng, C. H. Chem. Commun. 2013, 49, 8540. doi: 10.1039/c3ra40657a
	(h) Li, J.; Zheng, Y.; Yu, X. L.; Lv, S. Y.; Wang, Q. T.; Hai, L.; Wu Y. RSC Adv. 2015, 5, 103280. doi: 10.1039/c3ra40657a
	(i) Liu, Z.; Zhang, J.; Chen, S.; Shi, E.; Xu, Y.; Wan, X. Angew. Chem., Int. Ed. 2012, 51, 3231. doi: 10.1039/c3ra40657a
	(j) Meng, Q.; Wang, F.; Li, M. J. Mol. Model. 2013, 19, 2225. doi: 10.1039/c3ra40657a
[8]	Liao Y.-Y.; Gao Y.-C.; Zheng W.; Tang R.-Y. Adv. Synth. Catal. 2018, 360 3391. doi: 10.1002/adsc.201800592
[9]	Lollar C. T.; Krenek K. M.; Bruemmer K. J.; Lippert A. R. Org. Biomol. Chem. 2014, 12 406. doi: 10.1039/C3OB42024H
[10]	(a) Satish, G.; Polu, A.; Ramar, T.; Ilangovan, A. J. Org. Chem. 2015, 80, 5167. doi: 10.1021/acs.joc.5b00581
	(b) Reddy, M. R.; Rao, N. N.; Ramakrishna, K.; Meshram, H. M. Tetrahedron Lett. 2014, 55, 4758. doi: 10.1021/acs.joc.5b00581
	(c) Ilangovan, A.; Satish, G. J. Org. Chem. 2014, 79, 4984. doi: 10.1021/acs.joc.5b00581
	(d) Gao, F. F.; Xue, W. J.; Wang, J. G.; Wu, A. X. Tetrahedron 2014, 70, 4331. doi: 10.1021/acs.joc.5b00581
[11]	(a) Huang, P. C.; Gandeepan, P.; Cheng, C. H. Chem. Commun. 2013, 49, 8540. doi: 10.1039/c3cc44435j
	(b) Wu, H.; Zhang, Z. G.; Liu, Q. F.; Liu, T. X.; Ma, N. N.; Zhang, G. S. Org. Lett. 2018, 20, 2897. doi: 10.1039/c3cc44435j
	(c) Salvanna, N.; Reddy, L. M.; Kumar, R. A.; Das, B. ChemistrySelect 2018, 3, 8019. doi: 10.1039/c3cc44435j
[12]	Nobrega J. A.; Goncalves S. M. C.; Peppe C. Synth. Commun. 2002, 32 3711. doi: 10.1081/SCC-120015383
[13]	Shekhar A. C.; Kumar A. R.; Sathaiah G.; Paul V. L.; Sridhar M.; Rao P. S. Tetrahedron Lett. 2009, 50 7099. doi: 10.1016/j.tetlet.2009.10.006
[14]	Kirincich S. J.; Xiang J.; Green N.; Tam S.; Yang H. Y.; Shim J.; Clark J. D.; McKew J. C. Bioorg. Med. Chem. 2009, 17 4383. doi: 10.1016/j.bmc.2009.05.027
[15]	Luo J. F.; Gao S. S.; Ma Y. R.; Ge G. P. Synlett 2018, 29 969. doi: 10.1055/s-0036-1591904
[16]	Ji H. H.; Zhu Y. Z.; Shao Y.; Liu J.; Yuan Y.; Jia X. D. J. Org. Chem. 2017, 82 9859. doi: 10.1021/acs.joc.7b01480
[17]	Wang H. Y.; Wang K. Y.; Man Y. Q.; Gao X. N.; Yang L. M.; Ren Y. F.; Li N.; Tang B.; Zhao G. Adv. Synth. Catal. 2017, 359 3934. doi: 10.1002/adsc.201700649
[18]	Bredenkampa A.; Mohrb F.; Kirsch S. F. Synthesis 2015, 47 1937. doi: 10.1055/s-0034-1380517
[19]	Zhang C.; Li S.; Filip B.; Richmond L.; Ye X.; Jiang Z. ACS Catal. 2016, 6 10 6853. doi: 10.1021/acscatal.6b01969
[20]	Salvanna N.; Ramesh P.; Kumarc K. S.; Das B. New J. Chem. 2017, 41 13754. doi: 10.1039/C7NJ02441J


Entry	Cat.	Additive	Time/h	Yield^b/%
1	CuCl₂	None	49	34
2	CuCl	None	110	23
3	CuBr	None	110	17
4	CuI	None	82	N.R.
5	CuSCN	None	82	N.R.
6	CuCN	None	82	N.R.
7	Cu₂O	None	110	Trace
8	Cu(OAc)₂	None	66	N.R.
9	CuCl₂	ZnCl₂ (1 equiv.)	49	40
10	CuCl₂	AlCl₃ (1 equiv.)	49	N.R.
11	CuCl₂	BF₃·Et₂O (1 equiv.)	67	N.R.
12	CuCl₂	FeCl₃ (1 equiv.)	67	N.R.
13	CuCl₂	PdCl₂ (1 equiv.)	67	N.R.
14	CuCl₂	Cu(ClO₄)·6H₂O (1 equiv.)	67	N.R.
15	CuI	CoSO₄ (1 equiv.)	59	45
16	CuSCN	CoCl₂ (1 equiv.)	59	62
17	CuCN	Yb(OTf)₃ (1 equiv.)	48	N.R.
18	Cu₂O	Ni(OAc)₂·4H₂O (1 equiv.)	65	16
19	Cu(OAc)₂	Co(NO₃)₂·6H₂O (1 equiv.)	65	Trace
20	CuCl₂	Cu(OAc)₂·4H₂O (1 equiv.)	65	N.R.
21	CuCl₂	LiCl (1 equiv.)	49	N.R.
22	CuCl₂	CuCl₂(1 equiv.)	49	23
23	CuCl₂	CuCl₂(1 equiv.)+ PivOH (1 equiv.)	58	47
24	CuCl₂	CuCl₂(1 equiv.)+ PhCOOH (1 equiv.)	57	69
25	CuCl₂	CuCl₂(20 mol%)+PhCOOH (20 mol%)	84	78
26	None	CoCl₂ (1 equiv.)+PhCOOH (20 mol%)	77	N.R.


Entry	Cat.	Additive	Time/h	Yield^b/%
1	CuCl₂	None	49	34
2	CuCl	None	110	23
3	CuBr	None	110	17
4	CuI	None	82	N.R.
5	CuSCN	None	82	N.R.
6	CuCN	None	82	N.R.
7	Cu₂O	None	110	Trace
8	Cu(OAc)₂	None	66	N.R.
9	CuCl₂	ZnCl₂ (1 equiv.)	49	40
10	CuCl₂	AlCl₃ (1 equiv.)	49	N.R.
11	CuCl₂	BF₃·Et₂O (1 equiv.)	67	N.R.
12	CuCl₂	FeCl₃ (1 equiv.)	67	N.R.
13	CuCl₂	PdCl₂ (1 equiv.)	67	N.R.
14	CuCl₂	Cu(ClO₄)·6H₂O (1 equiv.)	67	N.R.
15	CuI	CoSO₄ (1 equiv.)	59	45
16	CuSCN	CoCl₂ (1 equiv.)	59	62
17	CuCN	Yb(OTf)₃ (1 equiv.)	48	N.R.
18	Cu₂O	Ni(OAc)₂·4H₂O (1 equiv.)	65	16
19	Cu(OAc)₂	Co(NO₃)₂·6H₂O (1 equiv.)	65	Trace
20	CuCl₂	Cu(OAc)₂·4H₂O (1 equiv.)	65	N.R.
21	CuCl₂	LiCl (1 equiv.)	49	N.R.
22	CuCl₂	CuCl₂(1 equiv.)	49	23
23	CuCl₂	CuCl₂(1 equiv.)+ PivOH (1 equiv.)	58	47
24	CuCl₂	CuCl₂(1 equiv.)+ PhCOOH (1 equiv.)	57	69
25	CuCl₂	CuCl₂(20 mol%)+PhCOOH (20 mol%)	84	78
26	None	CoCl₂ (1 equiv.)+PhCOOH (20 mol%)	77	N.R.

铜催化的有氧氧化合成靛红类衍生物的方法