Rh-Catalyzed gem-Difluoroallylation of N-Tosylhydrazones

doi:10.6023/cjoc202205054

Abstract

A rhodium-catalyzed rearrangement reaction of N-tosylhydrazones and 3,3-difluoroallyl sulfides was developed. This protocal provided a facile and efficient synthesis route to gem-difluoroallyl compounds with medium to excellent yield and good functional group tolerance. Moreover, the applicability of current method has been demonstrated by one-pot reaction, gram-scale synthesis and further transformations.

Key words: N-tosylhydrazones, 3,3-difluoroallyl sulfides, Rh-catalysis, gem-difluoroallylation

Cite this article

Jiazhuang Wang, Liguo Teng, Shaoqi Xiong, Tiebo Xiao, Yubo Jiang. Rh-Catalyzed gem-Difluoroallylation of N-Tosylhydrazones[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3658-3667.

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Entry	Catalyst	Base	Solvent	Temperature/℃	Yield^b/%
1	[Rh(OAc)₂]₂	Cs₂CO₃	DCE	100	30
2	[Rh(esp)]₂	Cs₂CO₃	DCE	100	81
3	[Rh(OPiv)₂]₂	Cs₂CO₃	DCE	100	48
4^c	Cu(MeCN)₄PF₆	Cs₂CO₃	DCE	100	0
5^c	AgSbF₆	Cs₂CO₃	DCE	100	20
6	[Rh(esp)]₂	LiO^tBu	DCE	100	53
7	[Rh(esp)]₂	NaO^tBu	DCE	100	51
8	[Rh(esp)]₂	K₂CO₃	DCE	100	62
9	[Rh(esp)]₂	K₃PO₄	DCE	100	36
10	[Rh(esp)]₂	Cs₂CO₃	MeCN	100	0
11	[Rh(esp)]₂	Cs₂CO₃	Dioxane	100	75
12	[Rh(esp)]₂	Cs₂CO₃	THF	100	69
13	[Rh(esp)]₂	Cs₂CO₃	DCE	90	70
14	[Rh(esp)]₂	Cs₂CO₃	DCE	110	80
15	[Rh(esp)]₂	Cs₂CO₃	DCE	120	49
16^d	[Rh(esp)]₂	Cs₂CO₃	DCE	100	78
17^e	[Rh(esp)]₂	Cs₂CO₃	DCE	100	72
18^f	[Rh(esp)]₂	Cs₂CO₃	DCE	100	80
19^g	[Rh(esp)]₂	Cs₂CO₃	DCE	100	76

Entry	Catalyst	Base	Solvent	Temperature/℃	Yield^b/%
1	[Rh(OAc)₂]₂	Cs₂CO₃	DCE	100	30
2	[Rh(esp)]₂	Cs₂CO₃	DCE	100	81
3	[Rh(OPiv)₂]₂	Cs₂CO₃	DCE	100	48
4^c	Cu(MeCN)₄PF₆	Cs₂CO₃	DCE	100	0
5^c	AgSbF₆	Cs₂CO₃	DCE	100	20
6	[Rh(esp)]₂	LiO^tBu	DCE	100	53
7	[Rh(esp)]₂	NaO^tBu	DCE	100	51
8	[Rh(esp)]₂	K₂CO₃	DCE	100	62
9	[Rh(esp)]₂	K₃PO₄	DCE	100	36
10	[Rh(esp)]₂	Cs₂CO₃	MeCN	100	0
11	[Rh(esp)]₂	Cs₂CO₃	Dioxane	100	75
12	[Rh(esp)]₂	Cs₂CO₃	THF	100	69
13	[Rh(esp)]₂	Cs₂CO₃	DCE	90	70
14	[Rh(esp)]₂	Cs₂CO₃	DCE	110	80
15	[Rh(esp)]₂	Cs₂CO₃	DCE	120	49
16^d	[Rh(esp)]₂	Cs₂CO₃	DCE	100	78
17^e	[Rh(esp)]₂	Cs₂CO₃	DCE	100	72
18^f	[Rh(esp)]₂	Cs₂CO₃	DCE	100	80
19^g	[Rh(esp)]₂	Cs₂CO₃	DCE	100	76

Rh催化N-磺酰腙的偕-二氟烯丙基化反应