铜催化的有氧氧化合成靛红类衍生物的方法

doi:10.6023/cjoc201903024

摘要/Abstract

研究了铜催化的脱羰环化生成靛红的方法，使用氧气作为最终的氧化剂.这个互补的C（sp³）—H官能团化方法为合成靛红提供了一种新方案.Cu/O₂/Co体系显示出良好的反应性和兼容性，富电子和缺电子的官能团都可以很好地兼容.并基于机理研究和以前的文献报道，提出了一个可能的假设机理.

关键词: 铜催化, 碳氢键活化, 靛红, 脱羰, 氧气

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

引用此文

AhmadMuhammad Siddique, 主亚敏, 郭云龙, 张赛赛, 沈增明. 铜催化的有氧氧化合成靛红类衍生物的方法[J]. 有机化学, 2019, 39(11): 3244-3249.

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.

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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.