Nickel-Catalyzed Stereoselective Aryl-Difluoroalkylation of Alkynes

doi:10.6023/cjoc202203054

Abstract

A nickel-catalyzed aryl-difluoroalkylation of alkynes is developed. A series of trisubstituted fluoroalkenes can be obtained in a highly stereoselective manner by mixing of simple starting materials alkynes, ethyl bromodifluoroacetate, and arylboronic acids in the presence of nickel catalyst. This method features low-cost catalyst, mild reaction conditions, and excellent functional group compatibility.

Key words: nickel catalysis, alkynes, stereoselective, aryl-difluoroalkylation, fluorine chemistry

Cite this article

Qi Sun, Zeying Sun, Ze Yu, Guangwei Wang. Nickel-Catalyzed Stereoselective Aryl-Difluoroalkylation of Alkynes[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2515-2520.

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Fig. & Tab. 5

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Entry	[Ni]	Ligand	Base	Solvent	Yield^b/%
1	NiCl₂(dppe)	tpy	K₃PO₄	DMF	3
2	NiBr₂(PPh₃)₂	tpy	K₃PO₄	DMF	2
3	NiCl₂(py)₄	tpy	K₃PO₄	DMF	15
4	NiCl₂(py)₄	tpy	Na₂CO₃	DMF	24
5	NiCl₂(py)₄	tpy	K₂CO₃	DMF	51
6	NiCl₂(py)₄	bpy	K₂CO₃	DMF	8
7	NiCl₂(py)₄	1,10-phen	K₂CO₃	DMF	3
8	NiCl₂(py)₄	xantphos	K₂CO₃	DMF	7
9	NiCl₂(py)₄	tpy	K₂CO₃	DCE	90 (72)
10	NiCl₂(py)₄	tpy	K₂CO₃	THF	52
11	NiCl₂(py)₄	tpy	K₂CO₃	MeCN	13
12	NiCl₂(py)₄	tpy	K₂CO₃	Tol	3

Entry	[Ni]	Ligand	Base	Solvent	Yield^b/%
1	NiCl₂(dppe)	tpy	K₃PO₄	DMF	3
2	NiBr₂(PPh₃)₂	tpy	K₃PO₄	DMF	2
3	NiCl₂(py)₄	tpy	K₃PO₄	DMF	15
4	NiCl₂(py)₄	tpy	Na₂CO₃	DMF	24
5	NiCl₂(py)₄	tpy	K₂CO₃	DMF	51
6	NiCl₂(py)₄	bpy	K₂CO₃	DMF	8
7	NiCl₂(py)₄	1,10-phen	K₂CO₃	DMF	3
8	NiCl₂(py)₄	xantphos	K₂CO₃	DMF	7
9	NiCl₂(py)₄	tpy	K₂CO₃	DCE	90 (72)
10	NiCl₂(py)₄	tpy	K₂CO₃	THF	52
11	NiCl₂(py)₄	tpy	K₂CO₃	MeCN	13
12	NiCl₂(py)₄	tpy	K₂CO₃	Tol	3

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