Visible-Light Promoted Bromotrifluoromethylation Reaction of CF3Br with Unactivated Alkenes

doi:10.6023/cjoc202604019

Abstract

A visible-light promoted bromotrifluoromethylation reaction of CF₃Br with unactivated alkenes was achieved in the presence of catalytic amount of fac-Ir^III(ppy)₃. In the reaction, CF₃Br serves as a bifunctional reagent to provide both the CF₃ group and bromine source. The method features high regioselectivity, mild reaction conditions, high atom economy and good yields, which offers an economical and practical method for the construction of structurally diverse β-trifluoromethylated alkyl bromides.

Key words: visible-light promotion, CF₃Br, unactivated alkenes, bromotrifluoromethylation, bifunctional trifluoromethylating reagents

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Mingqi Zhao, Danfeng Huang, Huan Wen, Dan Zhang, Kehu Wang, Junjiao Wang, Bosheng Zhang, Yulai Hu. Visible-Light Promoted Bromotrifluoromethylation Reaction of CF₃Br with Unactivated Alkenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3603-3614.

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Fig. & Tab. 10

References 25

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Entry	n(alkenes)/n(base)	Base	Solvent	Isolated yield/%
1	1.0/1.0	K₂CO₃	MeCN	61
2	1.0/1.5	K₂CO₃	MeCN	71
3	1.0/2.0	K₂CO₃	MeCN	96
4	1.0/2.5	K₂CO₃	MeCN	69
5^b	1.0/2.0	K₂CO₃	MeCN	82
6^c	1.0/2.0	K₂CO₃	MeCN	71
7^d	1.0/2.0	K₂CO₃	MeCN	84
8^e	1.0/2.0	K₂CO₃	MeCN	62
9	1.0/2.0	K₂CO₃	DMSO	N.R.^f
10	1.0/2.0	K₂CO₃	Acetone	48
11	1.0/2.0	K₂CO₃	DCM	N.R.
12	1.0/2.0	K₂CO₃	EtOAc	Trace
13	1.0/2.0	K₂CO₃	THF	22
14	1.0/2.0	K₂CO₃	1,4-Dioxane	Trace
15	1.0/2.0	Na₂CO₃	MeCN	87
16	1.0/2.0	NaHCO₃	MeCN	90
17	1.0/2.0	K₂HPO₄	MeCN	90
18	1.0/2.0	K₃PO₄	MeCN	76
19	1.0/2.0	DBU	MeCN	N.R.
20	1.0/2.0	TMEDA	MeCN	N.R.
21^g	1.0/2.0	K₂CO₃	MeCN	83
22^h	1.0/0.0	—	MeCN	7
23ⁱ	1.0/2.0	K₂CO₃	MeCN	N.R.
24^j	1.0/2.0	K₂CO₃	MeCN	N.R.

Entry	n(alkenes)/n(base)	Base	Solvent	Isolated yield/%
1	1.0/1.0	K₂CO₃	MeCN	61
2	1.0/1.5	K₂CO₃	MeCN	71
3	1.0/2.0	K₂CO₃	MeCN	96
4	1.0/2.5	K₂CO₃	MeCN	69
5^b	1.0/2.0	K₂CO₃	MeCN	82
6^c	1.0/2.0	K₂CO₃	MeCN	71
7^d	1.0/2.0	K₂CO₃	MeCN	84
8^e	1.0/2.0	K₂CO₃	MeCN	62
9	1.0/2.0	K₂CO₃	DMSO	N.R.^f
10	1.0/2.0	K₂CO₃	Acetone	48
11	1.0/2.0	K₂CO₃	DCM	N.R.
12	1.0/2.0	K₂CO₃	EtOAc	Trace
13	1.0/2.0	K₂CO₃	THF	22
14	1.0/2.0	K₂CO₃	1,4-Dioxane	Trace
15	1.0/2.0	Na₂CO₃	MeCN	87
16	1.0/2.0	NaHCO₃	MeCN	90
17	1.0/2.0	K₂HPO₄	MeCN	90
18	1.0/2.0	K₃PO₄	MeCN	76
19	1.0/2.0	DBU	MeCN	N.R.
20	1.0/2.0	TMEDA	MeCN	N.R.
21^g	1.0/2.0	K₂CO₃	MeCN	83
22^h	1.0/0.0	—	MeCN	7
23ⁱ	1.0/2.0	K₂CO₃	MeCN	N.R.
24^j	1.0/2.0	K₂CO₃	MeCN	N.R.

可见光驱动CF₃Br与未活化烯烃的溴-三氟甲基化反应研究

Visible-Light Promoted Bromotrifluoromethylation Reaction of CF₃Br with Unactivated Alkenes

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可见光驱动CF3Br与未活化烯烃的溴-三氟甲基化反应研究