Palladium-Catalyzed Asymmetric C—H Activation for the Synthesis of Planar Chiral Ferrocene Sulfonamides

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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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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

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

Palladium-Catalyzed Asymmetric C—H Activation for the Synthesis of Planar Chiral Ferrocene Sulfonamides

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Entry	R¹	R²	R³	R⁴	R⁵	Product	Yield^b/%
1	H	H	H	H	Me	2a	97
2	Me	H	H	H	Me	2b	93
3	H	Me	H	H	Me	2c	95
4	H	H	Me	H	Me	2d	93
5	H	H	H	Me	Me	2e	91
6	H	F	H	H	Me	2f	96
7	H	Cl	H	H	Me	2g	91
8	H	t-Bu	H	H	Me	2h	98
9	H	OMe	H	H	Me	2i	97
10	H	H	OMe	H	Me	2j	99
11	H	H	H	H	Bn	2k	91
12	F	H	H	H	Me	2l	89
13	Cl	H	H	H	Me	2m	89
14	OMe	H	H	H	Me	2n	96

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