基于钴催化吲哚酰胺与二炔和单炔的[4+2]环化反应合成γ-咔啉酮

doi:10.6023/cjoc202302018

摘要/Abstract

采用廉价易得的过渡金属钴盐为催化剂, 实现了3-吲哚甲酰胺与炔烃的C—H/N—H活化环化反应, 制备了一系列γ-咔啉酮类化合物. 实验表明反应的最佳条件为: 10 mol%乙酰丙酮钴为催化剂, 1.0 equiv.乙酰丙酮锰为氧化剂, 2.0 equiv.特戊酸钠为碱, 三氟乙醇为溶剂, 120 ℃搅拌24 h. 该方法具有良好的底物适用性, 各种芳基或烷基取代的1,3-丁二炔均可以在标准条件下与3-吲哚甲酰胺反应, 并以中等到良好的收率得到3-炔基取代的γ-咔啉酮类化合物. 此外, 当使用端炔和内炔作为环化试剂时, 反应也可以以较好的产率和较高的选择性得到目标产物. 该反应使用廉价金属钴和锰为催化体系, 不需要额外配体和吲哚氮保护基团, 为合成具有广泛应用价值的γ-咔啉酮类化合物提供了一种有机合成方法.

关键词: 钴催化, 吲哚甲酰胺, 炔烃, [4+2]环化, γ-咔啉酮

A cobalt-catalyzed annulation of the C(sp²)—H/N—H bond of 3-indolecarboxamides with alkynes assisted by 8-aminoquinoline is reported for the preparation of γ-carbolinones. The research results indicated that under the optimal reaction conditions, the isolated yield was up to 90% with Co(acac)₂ (10 mol%) as catalyst, Mn(acac)₃ (1.0 equiv.) as oxidant, NaOPiv (2.0 equiv.) as base, trifluoroethanol (2.0 mL) as solvent at 120 ℃ for 24 h. The protocol has a broad scope for alkynes. Both 1,4-diarylbuta-1,3-diynes and dialkyl diynes could react with N-(quinolin-8-yl)-1H-indole-3-carboxamide, giving the desired products in moderate to good yield. It was noteworthy that terminal and internal alkynes were found to be applicable to this transformation, affording the γ-carbolinones in good yield and high selectivity. This method has the advantages of applying cheap and commercially available cobalt and manganese salts as the catalytic system, requiring no additional ligands and indole nitrogen protecting groups, providing a new method for the synthesis of γ-carbolinone compounds with wide application value.

Key words: cobalt-catalysis, indole carboxamide, alkynes, [4+2] annulation, γ-carbolinones

引用此文

贝文峰, 潘健, 冉冬梅, 刘伊琳, 杨震, 冯若昆. 基于钴催化吲哚酰胺与二炔和单炔的[4+2]环化反应合成γ-咔啉酮[J]. 有机化学, 2023, 43(9): 3226-3238.

Wenfeng Bei, Jian Pan, Dongmei Ran, Yilin Liu, Zhen Yang, Ruokun Feng. Cobalt-Catalyzed [4+2] Annulation of Indole Carboxamide with Diynes and Monoacetylene: Direct Access to γ-Carbolinones[J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3226-3238.

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Entry	Yield^b/%	Entry	Yield^b/%
1	60	9	88 (6:1)
2	73	10	83 (6:1)
3	65	11	51 (>20:1)
4	62	12	46 (6:1)
5	41	13	48 (>20:1)
6	32	14	71
7	28	15	78 (4:1)
8	91 (2.5:1)

Entry	Yield^b/%	Entry	Yield^b/%
1	60	9	88 (6:1)
2	73	10	83 (6:1)
3	65	11	51 (>20:1)
4	62	12	46 (6:1)
5	41	13	48 (>20:1)
6	32	14	71
7	28	15	78 (4:1)
8	91 (2.5:1)