取代8-羟基喹啉钌络合物催化Friedländer反应合成喹啉衍生物

doi:10.6023/cjoc202210036

摘要/Abstract

Friedländer喹啉合成法是以邻胺基芳基醛或酮与有α-亚甲基的酮环化制备喹啉的反应, 报道了一种喹啉钌络合物催化Friedländer法合成喹啉的方法. 首先, 以8-羟基喹啉钌络合物为催化剂, 对模板反应邻氨基苯甲醇和苯乙酮合成2-苯基喹啉进行了反应条件优化实验. 重点对比研究了8-羟基喹啉钌络合物配体上不同取代基对反应收率的影响, 其中5-甲基-8-羟基喹啉(1e)钌络合物催化邻氨基苯甲醇和苯乙酮合成2-苯基喹啉获得了73%的最高收率. 结合IR, UV以及密度泛函理论(DFT)计算讨论了配体结构与催化性能之间的关系. 提出了β-H消除形成醛过渡态, 交叉aldol反应再亚胺环化, 最后脱水生成目标产物的可行机理. 以(1e)₃Ru为催化剂, 在优化的反应条件下进行了底物扩展研究, 以69%~94%的收率合成了32个不同取代的喹啉衍生物, 验证了方法的普适性.

关键词: 8-羟基喹啉钌络合物, 催化, Friedländer反应

The Friedländer quinoline synthesis method is a reaction of o-aminoaryl aldehyde or ketone with methyl ketone to obtain quinoline. In this paper, a method for synthesizing quinoline catalyzed by ruthenium complexes of quinoline was reported. Using 8-hydroxyquinoline ruthenium complex as catalyst, the reaction conditions were optimized. The effects of different substituents of 8-hydroxyquinoline ruthenium complexes on the reaction yield were comparatively studied. Among them, 5-methyl-8-hydroxyquinoline (1e) ruthenium complex catalyzed the synthesis of 2-phenylquinoline from o-aminobenzyl alcohol and acetophenone with the highest yield of 73%. The relationship between ligand structure and catalytic performance was discussed by combining IR, UV and density functional theory (DFT) calculations. A possible mechanism was proposed, which included the formation of aldehyde transition state through β-H elimination, cross aldol reaction, imination cyclization and finally dehydration to produce the target product. Using (1e)₃Ru as catalyst, 32 quinoline derivatives with different substitutions were synthesized with 69%~94% yields under the optimized reaction conditions, which confirmed the generality of this method.

Key words: ruthenium complexes of 8-hydroxyquinoline, catalysis, Friedländer reaction

引用此文

朱玥, 陈璐, 赵静, 孙庆荣, 杨维清, 付海燕, 马梦林. 取代8-羟基喹啉钌络合物催化Friedländer反应合成喹啉衍生物[J]. 有机化学, 2023, 43(7): 2528-2542.

Yue Zhu, Lu Chen, Jing Zhao, Qingrong Sun, Weiqing Yang, Haiyan Fu, Menglin Ma. Synthesis of Quinoline Derivatives by Friedländer Reaction Catalyzed by Ruthenium Complexes of Substituted 8-Hydroxyquinoline[J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2528-2542.

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参考文献 31

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Entry	Cat.	Conversion rate/%	Selectivity^b/%
1	—	0	0^c
2	(1a)₃Al	0	0^c
3	(1a)₂Cu	12	37
4	(1a)₃Ir	14	35
5	(1a)₂Pd	16	35
6	(1a)₃Ru	32	33

Entry	Cat.	Conversion rate/%	Selectivity^b/%
1	—	0	0^c
2	(1a)₃Al	0	0^c
3	(1a)₂Cu	12	37
4	(1a)₃Ir	14	35
5	(1a)₂Pd	16	35
6	(1a)₃Ru	32	33

Entry	n(2a)∶n(3a)	Atmosphere	Base (equiv.)	Cat. (C/S)	Temp./℃	Solvent	CR/%	Selectivity^a/%
1	1∶1.1	Air	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	32	33
2	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	40	43
3	1∶1.1	Ar	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	41	42
4	1∶1.1	N₂	—^b	(1a)₃Ru (0.1 mol%)	70	CH₃OH	0^c	0^b
5	1∶1.1	N₂	NaOH (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	50	26
6	1∶1.1	N₂	t-BuOK (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	40	33
7	1∶1.1	N₂	KOH (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	47	29
8	1∶1.1	N₂	K₂CO₃ (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	17	54
9	1∶1.1	N₂	Et₃N (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	2	1
10	1∶1.1	N₂	Pyridine (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	2	1
11	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	82	CH₃CN	29	44
12	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	67	Tetrahydrofuran	11	54
13	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	85	tert-Butanol	53	35
14	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	111	Toluene	57	51
15	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	102	1,4-Dioxane	32	60
16	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	100	DMSO	22	24
17	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	100	DMF	1	2
18	1∶1.2	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	53	56
19	1∶1.3	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	58	56
20	1∶1.4	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	59	57
21	1∶1.5	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	61	57
22	1∶1.6	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	59	57
23	1∶2.0	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	50	57
24	1∶1.2	N₂	CH₃ONa (1.1)	(1a)₃Ru (0.1 mol%)	110	Toluene	53	55
25	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.1 mol%)	110	Toluene	68	62
26	1∶1.2	N₂	CH₃ONa (1.4)	(1a)₃Ru (0.1 mol%)	110	Toluene	67	61
27	1∶1.2	N₂	CH₃ONa (1.5)	(1a)₃Ru (0.1 mol%)	110	Toluene	51	59
28	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.2 mol%)	110	Toluene	67	63
29	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.3 mol%)	110	Toluene	69	63
30	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.4 mol%)	110	Toluene	70	63
31	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.5 mol%)	110	Toluene	73	64
32	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (1.0 mol%)	110	Toluene	75	65
33	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (2.0 mol%)	110	Toluene	74	65
34	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.5 mol%)	20	Toluene	0^b	0^b
35	1∶1.52	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.5 mol%)	40	Toluene	64	63
36	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.5 mol%)	60	Toluene	74	70
37	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.5 mol%)	90	Toluene	77	64

Entry	n(2a)∶n(3a)	Atmosphere	Base (equiv.)	Cat. (C/S)	Temp./℃	Solvent	CR/%	Selectivity^a/%
1	1∶1.1	Air	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	32	33
2	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	40	43
3	1∶1.1	Ar	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	41	42
4	1∶1.1	N₂	—^b	(1a)₃Ru (0.1 mol%)	70	CH₃OH	0^c	0^b
5	1∶1.1	N₂	NaOH (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	50	26
6	1∶1.1	N₂	t-BuOK (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	40	33
7	1∶1.1	N₂	KOH (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	47	29
8	1∶1.1	N₂	K₂CO₃ (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	17	54
9	1∶1.1	N₂	Et₃N (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	2	1
10	1∶1.1	N₂	Pyridine (1.2)	(1a)₃Ru (0.1 mol%)	70	CH₃OH	2	1
11	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	82	CH₃CN	29	44
12	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	67	Tetrahydrofuran	11	54
13	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	85	tert-Butanol	53	35
14	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	111	Toluene	57	51
15	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	102	1,4-Dioxane	32	60
16	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	100	DMSO	22	24
17	1∶1.1	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	100	DMF	1	2
18	1∶1.2	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	53	56
19	1∶1.3	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	58	56
20	1∶1.4	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	59	57
21	1∶1.5	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	61	57
22	1∶1.6	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	59	57
23	1∶2.0	N₂	CH₃ONa (1.2)	(1a)₃Ru (0.1 mol%)	110	Toluene	50	57
24	1∶1.2	N₂	CH₃ONa (1.1)	(1a)₃Ru (0.1 mol%)	110	Toluene	53	55
25	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.1 mol%)	110	Toluene	68	62
26	1∶1.2	N₂	CH₃ONa (1.4)	(1a)₃Ru (0.1 mol%)	110	Toluene	67	61
27	1∶1.2	N₂	CH₃ONa (1.5)	(1a)₃Ru (0.1 mol%)	110	Toluene	51	59
28	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.2 mol%)	110	Toluene	67	63
29	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.3 mol%)	110	Toluene	69	63
30	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.4 mol%)	110	Toluene	70	63
31	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.5 mol%)	110	Toluene	73	64
32	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (1.0 mol%)	110	Toluene	75	65
33	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (2.0 mol%)	110	Toluene	74	65
34	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.5 mol%)	20	Toluene	0^b	0^b
35	1∶1.52	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.5 mol%)	40	Toluene	64	63
36	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.5 mol%)	60	Toluene	74	70
37	1∶1.2	N₂	CH₃ONa (1.3)	(1a)₃Ru (0.5 mol%)	90	Toluene	77	64

Entry	Compd.	IR/cm^－1		UV/nm	Catalytic performance
Entry	Compd.	Ru—O	C—O	UV/nm	CR/%	Selectivity/%
1	(1a)₃Ru	3372	527	431	74	70
2	(1b)₃Ru	3438	538	429	35	33
3	(1c)₃Ru	3286	540	428	17	18
4	(1e)₃Ru	3439	542	444	81	96
5	(1k)₃Ru	3444	548	443	78	92