镍催化(Z)-1,2-二芳硫基-1,2-二芳基烯烃与格氏试剂偶联反应制备多取代烯烃

doi:10.6023/cjoc201904050

摘要/Abstract

以5.0 mol% NiCl₂(dppe)作为催化剂, 催化(Z)-1,2-二芳硫基-1,2-二芳基烯烃和格氏试剂偶联反应, 高选择性制备了一系列多取代烯烃化合物. 有机硫基团经水解、氧化后生成二芳基二硫醚, 实现了硫资源的循环利用, 符合绿色化学要求. 同时, 此方法对不同取代的(Z)-1,2-二芳硫基-1,2-二芳基烯烃和格氏试剂均具有较好的适用性, 以较高的产率获得相应的目标产物, 为多取代烯烃的制备提供了有效的路径.

关键词: 镍催化偶联反应, 多取代烯烃, (Z)-1,2-二芳硫基-1,2-二芳基烯烃, 格氏试剂

A convenient protocol for the synthesis of multi-substituted alkenes from (Z)-1,2-diarylthio-1,2-diarylalkenes with Grignard reagents was developed via the highly selective coupling of (Z)-1,2-diarylthio-1,2-diarylalkenes catalyzed by 5.0 mol% NiCl₂(dppe). The leaving organosulfur group could be converted to diaryldisulfide after hydrolysis and oxidation, which realized the recycling of sulfur resources, meeting the requirements of green chemistry. This process tolerated to different (Z)-1,2-diarylthio-1,2-diarylalkenes and Grignard reagents to deliver products in good to excellent yields, providing an efficient route to multi-substituted alkenes.

Key words: nickel-catalyzed coupling, multi-substituted alkenes, (Z)-1,2-diarylthio-1,2-diarylalkenes, Grignard reagents

引用此文

吴燕, 罗凡, 潘世敏, 李玉涵, 何树华. 镍催化(Z)-1,2-二芳硫基-1,2-二芳基烯烃与格氏试剂偶联反应制备多取代烯烃[J]. 有机化学, 2019, 39(10): 2946-2951.

Wu, Yan, Luo, Fan, Pan, Shimin, Li, Yuhan, He, Shuhua. Nickel-Catalyzed Coupling of 1,2-Diarylthio-1,2-diarylalkenes with Grignard Reagents for Synthesis of Multi-substituted Alkenes[J]. Chinese Journal of Organic Chemistry, 2019, 39(10): 2946-2951.

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Entry	Catalyst (mol%)	Ligand (mol%)	Solvent	Temp./℃	Time/h	Yield^b/% of 3a
1	NiF₂ (25)	PPh₃ (25)	THF	80	6.0	21
2	NiF₂ (25)	dppe (25)	THF	80	6.0	34
3	NiF₂ (25)	PCy₃(25)	THF	80	6.0	Trace
4	NiCl₂ (25)	dppe (25)	THF	80	6.0	38
5	NiBr₂ (25)	dppe (25)	THF	80	6.0	32
6	Ni(acac)₂ (25)	dppe (25)	THF	80	6.0	Trace
7	Ni(OAc)₂ (25)	dppe (25)	THF	80	6.0	Trace
8	NiCl₂(PPh₃)₂ (25)	dppe (25)	THF	80	6.0	25
9	NiCl₂(dppe) (25)	—	THF	80	6.0	82
10	NiCl₂(dppe) (25)	—	Toluene	80	6.0	78
11	NiCl₂(dppe) (25)	—	DCM	80	6.0	62
12	NiCl₂(dppe) (25)	—	CH₃CN	80	6.0	74
13	NiCl₂(dppe) (10)	—	THF	80	6.0	65
14	NiCl₂(dppe) (10)	—	THF	120	6.0	60
15	NiCl₂(dppe) (10)	—	THF	80	8.0	72
16	NiCl₂(dppe) (10)	—	THF	80	12	81
17	NiCl₂(dppe) (5.0)	—	THF	80	20	89 (87)^c
18	NiCl₂(dppe) (1.0)	—	THF	80	30	48
19^d	NiCl₂(dppe) (5.0)	—	THF	80	20	89

Entry	Catalyst (mol%)	Ligand (mol%)	Solvent	Temp./℃	Time/h	Yield^b/% of 3a
1	NiF₂ (25)	PPh₃ (25)	THF	80	6.0	21
2	NiF₂ (25)	dppe (25)	THF	80	6.0	34
3	NiF₂ (25)	PCy₃(25)	THF	80	6.0	Trace
4	NiCl₂ (25)	dppe (25)	THF	80	6.0	38
5	NiBr₂ (25)	dppe (25)	THF	80	6.0	32
6	Ni(acac)₂ (25)	dppe (25)	THF	80	6.0	Trace
7	Ni(OAc)₂ (25)	dppe (25)	THF	80	6.0	Trace
8	NiCl₂(PPh₃)₂ (25)	dppe (25)	THF	80	6.0	25
9	NiCl₂(dppe) (25)	—	THF	80	6.0	82
10	NiCl₂(dppe) (25)	—	Toluene	80	6.0	78
11	NiCl₂(dppe) (25)	—	DCM	80	6.0	62
12	NiCl₂(dppe) (25)	—	CH₃CN	80	6.0	74
13	NiCl₂(dppe) (10)	—	THF	80	6.0	65
14	NiCl₂(dppe) (10)	—	THF	120	6.0	60
15	NiCl₂(dppe) (10)	—	THF	80	8.0	72
16	NiCl₂(dppe) (10)	—	THF	80	12	81
17	NiCl₂(dppe) (5.0)	—	THF	80	20	89 (87)^c
18	NiCl₂(dppe) (1.0)	—	THF	80	30	48
19^d	NiCl₂(dppe) (5.0)	—	THF	80	20	89

Entry	R¹	R²	R³	X	Product	Yield^b/%
1	Ph	Ph	Me	Cl	3a	87
2	Ph	4-MeC₆H₄	Me	Cl	3b	86
3	Ph	4-MeOC₆H₄	Me	Cl	3c	85
4	Ph	4-MeC₆H₄	Et	Cl	3d	86
5	3-ClC₆H₄	Ph	Et	Cl	3e	72
6	Ph	Ph	Et	Cl	3f	88
7	Ph	Ph	Ph	Br	4b	79
8	Ph	4-MeC₆H₄	Ph	Br	4b	72
9	4-FC₆H₄	Ph	Ph	Br	4c	63
10	Ph	Ph	4-MeC₆H₄	Br	4d	80
11	Ph	4-MeC₆H₄	4-MeC₆H₄	Br	4d	84
12	Ph	Ph	2-MeOC₆H₄	Br	4e	Trace^c
13	n-Pr	Ph	Ph	Br		N.R.^d
14	Ph	n-Pr	Ph	Br		N.R.

Entry	R¹	R²	R³	X	Product	Yield^b/%
1	Ph	Ph	Me	Cl	3a	87
2	Ph	4-MeC₆H₄	Me	Cl	3b	86
3	Ph	4-MeOC₆H₄	Me	Cl	3c	85
4	Ph	4-MeC₆H₄	Et	Cl	3d	86
5	3-ClC₆H₄	Ph	Et	Cl	3e	72
6	Ph	Ph	Et	Cl	3f	88
7	Ph	Ph	Ph	Br	4b	79
8	Ph	4-MeC₆H₄	Ph	Br	4b	72
9	4-FC₆H₄	Ph	Ph	Br	4c	63
10	Ph	Ph	4-MeC₆H₄	Br	4d	80
11	Ph	4-MeC₆H₄	4-MeC₆H₄	Br	4d	84
12	Ph	Ph	2-MeOC₆H₄	Br	4e	Trace^c
13	n-Pr	Ph	Ph	Br		N.R.^d
14	Ph	n-Pr	Ph	Br		N.R.