空气条件下温和高效催化N-吡啶吲哚啉的氧化脱氢

doi:10.6023/cjoc202009054

摘要/Abstract

报道了空气条件下温和高效的N-羟基邻苯二甲酰亚胺和铜共同催化N-吡啶吲哚啉的氧化脱氢反应. 已知的N-吡啶吲哚啉的氧化过程只能在过量强氧化剂2,3-二氯-5,6-二氰对苯醌存在下实现, 该反应以空气作为单一的氧化剂, 具有绿色、安全、低成本以及操作简便等优点, 为N-吡啶吲哚啉类化合物氧化生成相应吲哚衍生物提供了一条新的绿色途径.

关键词: N-羟基邻苯二甲酰亚胺, 脱氢, N-吡啶吲哚啉, 空气条件, 氧化反应

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

引用此文

唐灏, 张贝贝, 陈卫东, 骆钧飞. 空气条件下温和高效催化N-吡啶吲哚啉的氧化脱氢[J]. 有机化学, 2021, 41(3): 1131-1137.

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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图/表 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

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