Visible-Light Induced Iron-Catalyzed Hydroxymethylation of N-Heterocycles

doi:10.6023/cjoc202312025

Abstract

A new strategy for iron-catalyzed visible-light induced hydroxymethylation of N-heterocycles with methanol under mild conditions was developed. By employing FeCl₃ as the catalyst, 2-methylisonicotinic acid as the ligand, TsOH as the acid, air as the oxidant, and aqueous MeOH as the solvent, varieties of substituted quinolines, isoquinolines, pyridines, benzothiazole and voriconazole were hydroxymethylated smoothly in good to excellent yields, exhibiting good substrate scope. This strategy features green reaction conditions, excellent atom-economy and simple operations. It has potential applicable value in late-stage structure modification of drug molecule.

Key words: iron catalysis, hydroxymethylation, visible-light catalysis, N-heterocycle

Cite this article

Yanhua Fu, Chang Xu, Chao Zhang, Yisha Wang, Gaofeng Feng. Visible-Light Induced Iron-Catalyzed Hydroxymethylation of N-Heterocycles[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2265-2273.

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Entry	Iron catalyst	Ligand	Oxidant	Acid	Solvent	Wavelength/nm	Yield^b/%
1	FeCl₃	L1	NaBrO₃	TsOH	MeOH	390	38
2	FeCl₃	L1	NaBrO₃	CF₃COOH	MeOH	390	8
3	FeCl₃	L1	NaBrO₃	H₂SO₄ (98%)	MeOH	390	9
4	FeCl₃	L1	NaBrO₃	HCl (36%)	MeOH	390	13
5	FeCl₃	L1	NaBrO₃	HNO₃ (63%)	MeOH	390	9
6	FeCl₃	L1	None	TsOH	MeOH	390	25
7	FeCl₃	L1	O₂	TsOH	MeOH	390	30
8	FeCl₃	L1	NaIO₄	TsOH	MeOH	390	5
9	FeCl₃	L1	t-BuOOH	TsOH	MeOH	390	Trace
10	FeCl₃	L1	Air	TsOH	MeOH	390	61
11	FeCl₃	L5	Air	TsOH	MeOH	390	62
12	FeCl₃	L3	Air	TsOH	MeOH	390	51
13	FeCl₃	L4	Air	TsOH	MeOH	390	32
14	FeCl₃	L2	Air	TsOH	MeOH	390	73
15	FeCl₃	L2	Air	TsOH	MeOH	427	81
16	Fe[Fe(CN)₆]	L2	Air	TsOH	MeOH	427	5
17	Fe(acac)₃	L2	Air	TsOH	MeOH	427	nr^c
18	K₃Fe(CN)₆	L2	Air	TsOH	MeOH	427	nr^c
19	FeC₂O₄	L2	Air	TsOH	MeOH	427	23
20	FePO₄•H₂O	L2	Air	TsOH	MeOH	427	22
21	FeCl₃	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	427	94
22	FeCl₃	L2	Air	TsOH	MeOH/DMSO (V∶V=1∶1)	427	13
23	FeCl₃	L2	Air	TsOH	MeOH/MeCN (V∶V=1∶1)	427	15
24	FeCl₃	L2	Air	TsOH	MeOH/DCE (V∶V=1∶1)	427	15
25	FeCl₃	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	440	72
26	FeCl₃	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	LED^d	58
27	—	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	427	nr^c
28	FeCl₃	—	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	427	60
29	FeCl₃	L2	Air	—	MeOH/H₂O (V∶V=10∶1)	427	nr^c
30	FeCl₃	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	dark	nr^c
31	FeCl₃	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	Dark, 80 ℃	nr^c

Entry	Iron catalyst	Ligand	Oxidant	Acid	Solvent	Wavelength/nm	Yield^b/%
1	FeCl₃	L1	NaBrO₃	TsOH	MeOH	390	38
2	FeCl₃	L1	NaBrO₃	CF₃COOH	MeOH	390	8
3	FeCl₃	L1	NaBrO₃	H₂SO₄ (98%)	MeOH	390	9
4	FeCl₃	L1	NaBrO₃	HCl (36%)	MeOH	390	13
5	FeCl₃	L1	NaBrO₃	HNO₃ (63%)	MeOH	390	9
6	FeCl₃	L1	None	TsOH	MeOH	390	25
7	FeCl₃	L1	O₂	TsOH	MeOH	390	30
8	FeCl₃	L1	NaIO₄	TsOH	MeOH	390	5
9	FeCl₃	L1	t-BuOOH	TsOH	MeOH	390	Trace
10	FeCl₃	L1	Air	TsOH	MeOH	390	61
11	FeCl₃	L5	Air	TsOH	MeOH	390	62
12	FeCl₃	L3	Air	TsOH	MeOH	390	51
13	FeCl₃	L4	Air	TsOH	MeOH	390	32
14	FeCl₃	L2	Air	TsOH	MeOH	390	73
15	FeCl₃	L2	Air	TsOH	MeOH	427	81
16	Fe[Fe(CN)₆]	L2	Air	TsOH	MeOH	427	5
17	Fe(acac)₃	L2	Air	TsOH	MeOH	427	nr^c
18	K₃Fe(CN)₆	L2	Air	TsOH	MeOH	427	nr^c
19	FeC₂O₄	L2	Air	TsOH	MeOH	427	23
20	FePO₄•H₂O	L2	Air	TsOH	MeOH	427	22
21	FeCl₃	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	427	94
22	FeCl₃	L2	Air	TsOH	MeOH/DMSO (V∶V=1∶1)	427	13
23	FeCl₃	L2	Air	TsOH	MeOH/MeCN (V∶V=1∶1)	427	15
24	FeCl₃	L2	Air	TsOH	MeOH/DCE (V∶V=1∶1)	427	15
25	FeCl₃	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	440	72
26	FeCl₃	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	LED^d	58
27	—	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	427	nr^c
28	FeCl₃	—	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	427	60
29	FeCl₃	L2	Air	—	MeOH/H₂O (V∶V=10∶1)	427	nr^c
30	FeCl₃	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	dark	nr^c
31	FeCl₃	L2	Air	TsOH	MeOH/H₂O (V∶V=10∶1)	Dark, 80 ℃	nr^c

可见光诱导铁催化氮杂环的羟甲基化