Pd-Catalyzed Reductive Cross-Coupling of Allylic Esters with Aryl Iodides Involving the Insertion of SO2

doi:10.6023/cjoc202404019

Abstract

A Pd-catalyzed electrophilic-electrophilic reductive cross-coupling of allylic esters with aryl iodides involving the insertion of SO₂ has been reported. This reaction employs manganese powder as reductant, cheap and readily available sodium metabisulfite as SO₂ substitute, and features good reactivity, high rselectivity and broad substrate scope.

Key words: palladium-catalysis, reductive cross-coupling, allylic ester, sodium metabisulfite, sulfur dioxide

Cite this article

Xinwei Zhang, Shuizhen Lin, Xiaolei Huang. Pd-Catalyzed Reductive Cross-Coupling of Allylic Esters with Aryl Iodides Involving the Insertion of SO₂[J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3456-3466.

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Fig. & Tab. 7

References 12

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Entry	[SO₂]	[Pd]	L	Reductant	Base	Solvent	Yield^b/%
1	DABSO	Pd₂(dba)₃	PPh₃	Mn	NaOH	DMSO	42
2	Na₂S₂O₄	Pd₂(dba)₃	PPh₃	Mn	NaOH	DMSO	40
3	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	DMSO	45
4	K₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	DMSO	42
5	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	DMF	33
6	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	THF	0
7	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	DCE	0
8	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	Toluene	0
9	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOAc	DMSO	15
10	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	Na₂CO₃	DMSO	18
11	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaHCO₃	DMSO	50
12	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	K₃PO₄	DMSO	9
13	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	K₂HPO₄	DMSO	23
14	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	KH₂PO₄	DMSO	70
15	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	DMAP	DMSO	25
16	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	DIPEA	DMSO	21
17	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	Py	DMSO	23
18	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Zn	KH₂PO₄	DMSO	40
19	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Sn	KH₂PO₄	DMSO	35
20	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mg	KH₂PO₄	DMSO	0
21	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Fe	KH₂PO₄	DMSO	0
22	Na₂S₂O₅	Pd₂(dba)₃	L1	Mn	KH₂PO₄	DMSO	20
23	Na₂S₂O₅	Pd₂(dba)₃	L2	Mn	KH₂PO₄	DMSO	23
24	Na₂S₂O₅	Pd₂(dba)₃	PCy₃	Mn	KH₂PO₄	DMSO	59
25	Na₂S₂O₅	Pd₂(dba)₃	BINAP	Mn	KH₂PO₄	DMSO	30
26	Na₂S₂O₅	Pd₂(dba)₃	dppb	Mn	KH₂PO₄	DMSO	45
27	Na₂S₂O₅	Pd₂(dba)₃	dppf	Mn	KH₂PO₄	DMSO	22
28	Na₂S₂O₅	Pd(OAc)₂	PPh₃	Mn	KH₂PO₄	DMSO	45
29	Na₂S₂O₅	PdCl₂	PPh₃	Mn	KH₂PO₄	DMSO	42
30	Na₂S₂O₅	Pd(dba)₂	PPh₃	Mn	KH₂PO₄	DMSO	65
31^c	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	KH₂PO₄	DMSO	90
32^d	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	KH₂PO₄	DMSO	82

Entry	[SO₂]	[Pd]	L	Reductant	Base	Solvent	Yield^b/%
1	DABSO	Pd₂(dba)₃	PPh₃	Mn	NaOH	DMSO	42
2	Na₂S₂O₄	Pd₂(dba)₃	PPh₃	Mn	NaOH	DMSO	40
3	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	DMSO	45
4	K₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	DMSO	42
5	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	DMF	33
6	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	THF	0
7	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	DCE	0
8	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOH	Toluene	0
9	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaOAc	DMSO	15
10	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	Na₂CO₃	DMSO	18
11	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	NaHCO₃	DMSO	50
12	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	K₃PO₄	DMSO	9
13	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	K₂HPO₄	DMSO	23
14	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	KH₂PO₄	DMSO	70
15	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	DMAP	DMSO	25
16	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	DIPEA	DMSO	21
17	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	Py	DMSO	23
18	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Zn	KH₂PO₄	DMSO	40
19	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Sn	KH₂PO₄	DMSO	35
20	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mg	KH₂PO₄	DMSO	0
21	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Fe	KH₂PO₄	DMSO	0
22	Na₂S₂O₅	Pd₂(dba)₃	L1	Mn	KH₂PO₄	DMSO	20
23	Na₂S₂O₅	Pd₂(dba)₃	L2	Mn	KH₂PO₄	DMSO	23
24	Na₂S₂O₅	Pd₂(dba)₃	PCy₃	Mn	KH₂PO₄	DMSO	59
25	Na₂S₂O₅	Pd₂(dba)₃	BINAP	Mn	KH₂PO₄	DMSO	30
26	Na₂S₂O₅	Pd₂(dba)₃	dppb	Mn	KH₂PO₄	DMSO	45
27	Na₂S₂O₅	Pd₂(dba)₃	dppf	Mn	KH₂PO₄	DMSO	22
28	Na₂S₂O₅	Pd(OAc)₂	PPh₃	Mn	KH₂PO₄	DMSO	45
29	Na₂S₂O₅	PdCl₂	PPh₃	Mn	KH₂PO₄	DMSO	42
30	Na₂S₂O₅	Pd(dba)₂	PPh₃	Mn	KH₂PO₄	DMSO	65
31^c	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	KH₂PO₄	DMSO	90
32^d	Na₂S₂O₅	Pd₂(dba)₃	PPh₃	Mn	KH₂PO₄	DMSO	82

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钯催化SO₂插入的烯丙基酯与芳基碘化物的还原偶联反应

Pd-Catalyzed Reductive Cross-Coupling of Allylic Esters with Aryl Iodides Involving the Insertion of SO₂

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钯催化SO2插入的烯丙基酯与芳基碘化物的还原偶联反应