Palladium-Catalyzed Thiazole-Directed mono-Selective C(sp2)-H Bond Iodination Reaction

doi:10.6023/cjoc201904062

Abstract

A palladium-catalyzed ortho-C(sp²)-H bond iodination of 4-arylthiazoles has been developed. Through screening of directing groups and optimazation of reaction parameters, the most efficient reaction conditions for mono-ortho-position iodination were obtained, which were applied to synthesize a series of 4-(2-iodoaryl)thiazoles with broad scope of 4-aryl-thiazole substrates. Furthermore, the iodine group can be easily transformed into other organic functional groups, which improved the application value of this methodology. At last, plausible mechanism was proposed based on an intermolecular deuterium labeling kinetic experiment and radical inhibition experiments.

Key words: palladium-catalyzed, 4-arylthiazoles, mono-selectivity, C(sp²)-H bond, iodination

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Xing Lihao, Shao Lingyan, Fu Xiaopan, Deng Kezuan, Yang Jinyue, Ji Yafei. Palladium-Catalyzed Thiazole-Directed mono-Selective C(sp²)-H Bond Iodination Reaction[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3154-3161.

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Fig. & Tab. 9

References 19

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Entry	Catalyst	NIS (equiv.)	Solvent	Yield^b/%
1	None	2.0	DCE/HFIP	(V:V＝4:1)	0
2	Pd(OAc)₂	2.0	DCE/HFIP	(V:V＝4:1)	76
3	Pd(CH₃CN)₂Cl₂	2.0	DCE/HFIP	(V:V＝4:1)	64
4	Pd(TFA)₂	2.0	DCE/HFIP	(V:V＝4:1)	57
5	PdCl₂	2.0	DCE/HFIP	(V:V＝4:1)	38
6	Pd(PPh₃)₂Cl₂	2.0	DCE/HFIP	(V:V＝4:1)	27
7^c	Pd(OAc)₂	2.0	DCE/HFIP	(V:V＝4:1)	58
8^d	Pd(OAc)₂	2.0	DCE/HFIP	(V:V＝4:1)	75
9	Pd(OAc)₂	2.0	DCE	86
10	Pd(OAc)₂	2.0	HFIP	69
11	Pd(OAc)₂	2.0	DMF	85
12	Pd(OAc)₂	2.0	DCM	62
13	Pd(OAc)₂	2.0	TCM	21
14	Pd(OAc)₂	1.5	DCE	76
15	Pd(OAc)₂	2.5	DCE	93
16	Pd(OAc)₂	3.0	DCE	92
17^e	Pd(OAc)₂	2.5	DCE	78
18^f	Pd(OAc)₂	2.5	DCE	90


Entry	Catalyst	NIS (equiv.)	Solvent	Yield^b/%
1	None	2.0	DCE/HFIP	(V:V＝4:1)	0
2	Pd(OAc)₂	2.0	DCE/HFIP	(V:V＝4:1)	76
3	Pd(CH₃CN)₂Cl₂	2.0	DCE/HFIP	(V:V＝4:1)	64
4	Pd(TFA)₂	2.0	DCE/HFIP	(V:V＝4:1)	57
5	PdCl₂	2.0	DCE/HFIP	(V:V＝4:1)	38
6	Pd(PPh₃)₂Cl₂	2.0	DCE/HFIP	(V:V＝4:1)	27
7^c	Pd(OAc)₂	2.0	DCE/HFIP	(V:V＝4:1)	58
8^d	Pd(OAc)₂	2.0	DCE/HFIP	(V:V＝4:1)	75
9	Pd(OAc)₂	2.0	DCE	86
10	Pd(OAc)₂	2.0	HFIP	69
11	Pd(OAc)₂	2.0	DMF	85
12	Pd(OAc)₂	2.0	DCM	62
13	Pd(OAc)₂	2.0	TCM	21
14	Pd(OAc)₂	1.5	DCE	76
15	Pd(OAc)₂	2.5	DCE	93
16	Pd(OAc)₂	3.0	DCE	92
17^e	Pd(OAc)₂	2.5	DCE	78
18^f	Pd(OAc)₂	2.5	DCE	90

钯催化噻唑定位基导向的单选择性C(sp²)-H键碘化反应

Palladium-Catalyzed Thiazole-Directed mono-Selective C(sp²)-H Bond Iodination Reaction

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钯催化噻唑定位基导向的单选择性C(sp2)-H键碘化反应