镁促进未保护的吲哚及喹喔啉衍生物的选择性还原

doi:10.6023/cjoc202508021

摘要/Abstract

发展了一种以廉价的碱土金属镁为催化剂, 氨硼烷(H₃N•BH₃)作为氢源, 对未保护的吲哚、喹喔啉、苯并噁唑、苯并噻唑、喹啉及其衍生物进行选择性氢化的方法, 高效合成了一系列脂环族杂环化合物, 并获得了良好的产率. 该催化体系还适用于克级合成, 对氟、氯、溴、三氟甲基和羟基等官能团均表现出良好的兼容性. 氘代实验表明, 氨硼烷中的BH₃作为氢源, 而硼烷中的NH₃作为质子源. 该方法为二氢吲哚及四氢喹喔啉等部分饱和杂环衍生物的合成提供了新的途径.

关键词: 还原, 镁, 吲哚, 喹喔啉, 氨硼烷

This study present a transfer hydrogenation method employing ammonia borane (H₃N•BH₃) as the hydrogen source and inexpensive magnesium as the catalyst for the selective reduction of unprotected indoles, quinoxalines, benzoxazole, benzothiazole, quinolines, and their derivatives, resulting the corresponding alicyclic heterocyclic compounds with desirable yields. This catalytic system is applicable to gram-scale syntheses and demonstrates compatibility with various functional groups, including fluorine, chlorine, bromine, trifluoromethyl, and hydroxyl. Deuterium labeling experiments show that the BH₃ counterpart of NH₃•BH₃ served as the hydride source, while the NH₃ counterpart of ammonia borane acted as a proton source. It offers a novel approach for the preparation of partially saturated heterocyclic derivatives.

Key words: reduction, magnesium, indoles, quinoxalines, ammonia borane

引用此文

韦娜娜, 郭婉真, 鲁星, 任志强, 马豪杰, 张玉琦, 王记江, 韩波. 镁促进未保护的吲哚及喹喔啉衍生物的选择性还原[J]. 有机化学, 2026, 46(3): 1027-1038.

Nana Wei, Wanzhen Guo, Xing Lu, Zhiqiang Ren, Haojie Ma, Yuqi Zhang, Jijiang Wang, Bo Han. Magnesium-Promoted Selectively Reduction of Unprotected Indoles and Quinoxalines[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 1027-1038.

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参考文献 37

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Entry	Catalyst (mol%)	AB/equiv.	Solvent	Temp./℃	2a/%
1	MgCl₂ (10)	2.0	Toluene	80	49
2	MgSO₄ (10)	2.0	Toluene	80	52
3	Mg(OTf)₂ (10)	2.0	Toluene	80	40
4	MgI₂ (10)	2.0	Toluene	80	37
5	Mg (50)	2.0	Toluene	80	75
6	Zn (50)	2.0	Toluene	80	50
7	Al (50)	2.0	Toluene	80	40
8	Mn (50)	2.0	Toluene	80	45
9	Mg (50)	2.0	Et₂O	80	24
10	Mg (50)	2.0	THF	80	nd^b
11	Mg (50)	2.0	CH₂Cl₂	80	43
12	Mg (50)	2.0	CH₃CN	80	Trace
13	Mg (50)	2.0	Toluene	100	77
14	Mg (50)	2.0	Toluene	120	78
15	Mg (50)	3.0	Toluene	80	85
16	Mg (50)	4.0	Toluene	80	83
17^c	Mg (50)	3.0	Toluene	80	71
18	Mg (40)	3.0	Toluene	80	80
19	Mg (30)	3.0	Toluene	80	77
20	—	3.0	Toluene	80	14

Entry	Catalyst (mol%)	AB/equiv.	Solvent	Temp./℃	2a/%
1	MgCl₂ (10)	2.0	Toluene	80	49
2	MgSO₄ (10)	2.0	Toluene	80	52
3	Mg(OTf)₂ (10)	2.0	Toluene	80	40
4	MgI₂ (10)	2.0	Toluene	80	37
5	Mg (50)	2.0	Toluene	80	75
6	Zn (50)	2.0	Toluene	80	50
7	Al (50)	2.0	Toluene	80	40
8	Mn (50)	2.0	Toluene	80	45
9	Mg (50)	2.0	Et₂O	80	24
10	Mg (50)	2.0	THF	80	nd^b
11	Mg (50)	2.0	CH₂Cl₂	80	43
12	Mg (50)	2.0	CH₃CN	80	Trace
13	Mg (50)	2.0	Toluene	100	77
14	Mg (50)	2.0	Toluene	120	78
15	Mg (50)	3.0	Toluene	80	85
16	Mg (50)	4.0	Toluene	80	83
17^c	Mg (50)	3.0	Toluene	80	71
18	Mg (40)	3.0	Toluene	80	80
19	Mg (30)	3.0	Toluene	80	77
20	—	3.0	Toluene	80	14