钯催化不对称碳氢键活化合成平面手性二茂铁磺酰胺化合物

doi:10.6023/cjoc202404002

摘要/Abstract

研究了钯催化下N-(2-溴芳基)-N-烷基二茂铁磺酰胺分子内不对称C—H键芳基化反应, 以优异的收率和最高90%的ee值合成了一系列新型的平面手性二茂铁磺酰胺化合物.

Pd-catalyzed asymmetric synthesis of planar chiral ferrocenes by enantioselective intramolecular C—H arylation of N-(2-bromoaryl)-N-alkylferrocenesulfonamide were efficiently achieved in good enantioselectivities (up to 90% ee) and high yields.

Key words: palladium catalysis, plane chirality, ferrocene, sulfonamide, C—H bond activation

引用此文

张朝威, 徐兵斌, 刘文龙, 赵敬, 段伟良. 钯催化不对称碳氢键活化合成平面手性二茂铁磺酰胺化合物[J]. 有机化学, 2025, 45(2): 707-716.

Chaowei Zhang, Bingbin Xu, Wenlong Liu, Jing Zhao, Weiliang Duan. Palladium-Catalyzed Asymmetric C—H Activation for the Synthesis of Planar Chiral Ferrocene Sulfonamides[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 707-716.

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参考文献 20

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Entry		Base	Solvent	Yield^b/%
1	PPh₃	K₂CO₃	Dioxane	55
2	PCy₃HBF₄	K₂CO₃	Dioxane	48
3	P(t-Bu)₃HBF₄	K₂CO₃	Dioxane	5
4	PPh₃	Cs₂CO₃	Dioxane	97
5	PPh₃	Na₂CO₃	Dioxane	35
6^c	PPh₃	NaOPiv	Dioxane	—
7^c	PPh₃	CsOPiv	Dioxane	85
8^c	PPh₃	Cs₂CO₃	Dioxane	—
8	PPh₃	Cs₂CO₃	Toluene	20
9	PPh₃	Cs₂CO₃	1,2-Dichloroethane	90
10	PPh₃	Cs₂CO₃	t-Amyl-OH	90

Entry		Base	Solvent	Yield^b/%
1	PPh₃	K₂CO₃	Dioxane	55
2	PCy₃HBF₄	K₂CO₃	Dioxane	48
3	P(t-Bu)₃HBF₄	K₂CO₃	Dioxane	5
4	PPh₃	Cs₂CO₃	Dioxane	97
5	PPh₃	Na₂CO₃	Dioxane	35
6^c	PPh₃	NaOPiv	Dioxane	—
7^c	PPh₃	CsOPiv	Dioxane	85
8^c	PPh₃	Cs₂CO₃	Dioxane	—
8	PPh₃	Cs₂CO₃	Toluene	20
9	PPh₃	Cs₂CO₃	1,2-Dichloroethane	90
10	PPh₃	Cs₂CO₃	t-Amyl-OH	90

Entry		Ligand	Additive	T/℃	Catalyst	Yield^b/%	ee^d/%
1	Dioxane	L1	PivOH	100	Pd(OAc)₂	34	40
2	1,2-Dichloroethane	L1	PivOH	100	Pd(OAc)₂	75	50
3	p-Xylene	L1	PivOH	100	Pd(OAc)₂	14	74
4	N,N-Dimethylformamide	L1	PivOH	100	Pd(OAc)₂	Trace	35
5	Toluene	L1	PivOH	100	Pd(OAc)₂	14	75
6	t-Amyl-OH	L1	PivOH	100	Pd(OAc)₂	88	65
7	t-Amyl-OH	L2	PivOH	100	Pd(OAc)₂	75	62
8	t-Amyl-OH	L3	PivOH	100	Pd(OAc)₂	27	30
9	t-Amyl-OH	L4	PivOH	100	Pd(OAc)₂	50	57
10	t-Amyl-OH	L5	PivOH	100	Pd(OAc)₂	55	60
11	t-Amyl-OH	L6	PivOH	100	Pd(OAc)₂	39	70
12	t-Amyl-OH	L7	PivOH	100	Pd(OAc)₂	5	30
13	t-Amyl-OH	L8	PivOH	100	Pd(OAc)₂	27	0
14	t-Amyl-OH	L9	PivOH	100	Pd(OAc)₂	14	0
15	t-Amyl-OH	(R)-BINAP	PivOH	100	Pd(OAc)₂	58	20
16	t-Amyl-OH	(R)-SEGPhos	PivOH	100	Pd(OAc)₂	40	33
17^c	t-Amyl-OH	L1	PivOH	100	Pd(OAc)₂	82	78
18^c	t-Amyl-OH	L1	AdCOOH	100	Pd(OAc)₂	75	68
19^c	t-Amyl-OH	L1	PivOH	80	Pd(OAc)₂	55	79
20^c	t-Amyl-OH	L1	PivOH	120	Pd(OAc)₂	85	60
21^c	t-Amyl-OH	L1	PivOH	100	C₃H₅CpPd	85	76
22^c	t-Amyl-OH	L1	AdCOOH	100	C₃H₅CpPd	71	62
23^c	t-Amyl-OH	L1	PivOH	100	Pd₂(dba)₃	58	74

Entry		Ligand	Additive	T/℃	Catalyst	Yield^b/%	ee^d/%
1	Dioxane	L1	PivOH	100	Pd(OAc)₂	34	40
2	1,2-Dichloroethane	L1	PivOH	100	Pd(OAc)₂	75	50
3	p-Xylene	L1	PivOH	100	Pd(OAc)₂	14	74
4	N,N-Dimethylformamide	L1	PivOH	100	Pd(OAc)₂	Trace	35
5	Toluene	L1	PivOH	100	Pd(OAc)₂	14	75
6	t-Amyl-OH	L1	PivOH	100	Pd(OAc)₂	88	65
7	t-Amyl-OH	L2	PivOH	100	Pd(OAc)₂	75	62
8	t-Amyl-OH	L3	PivOH	100	Pd(OAc)₂	27	30
9	t-Amyl-OH	L4	PivOH	100	Pd(OAc)₂	50	57
10	t-Amyl-OH	L5	PivOH	100	Pd(OAc)₂	55	60
11	t-Amyl-OH	L6	PivOH	100	Pd(OAc)₂	39	70
12	t-Amyl-OH	L7	PivOH	100	Pd(OAc)₂	5	30
13	t-Amyl-OH	L8	PivOH	100	Pd(OAc)₂	27	0
14	t-Amyl-OH	L9	PivOH	100	Pd(OAc)₂	14	0
15	t-Amyl-OH	(R)-BINAP	PivOH	100	Pd(OAc)₂	58	20
16	t-Amyl-OH	(R)-SEGPhos	PivOH	100	Pd(OAc)₂	40	33
17^c	t-Amyl-OH	L1	PivOH	100	Pd(OAc)₂	82	78
18^c	t-Amyl-OH	L1	AdCOOH	100	Pd(OAc)₂	75	68
19^c	t-Amyl-OH	L1	PivOH	80	Pd(OAc)₂	55	79
20^c	t-Amyl-OH	L1	PivOH	120	Pd(OAc)₂	85	60
21^c	t-Amyl-OH	L1	PivOH	100	C₃H₅CpPd	85	76
22^c	t-Amyl-OH	L1	AdCOOH	100	C₃H₅CpPd	71	62
23^c	t-Amyl-OH	L1	PivOH	100	Pd₂(dba)₃	58	74