Synthesis of Selenylated Maleimides and Alkenes via Bromide Catalysis

doi:10.6023/cjoc202506004

Abstract

A highly efficient and metal-free catalytic system for the synthesis of various selenylated maleimides and alkene derivatives via ammonium bromide-catalyzed direct selenylation of C(sp²)—H bond in maleimides and 1,1-diaryl alkenes using elemental selenium and boronic acids as the selenyl source is developed. Simple catalytic conditions, wide substrate scope, good functional group compatibility, scalable-up, and easy operation are presented in this strategy. The preliminary mechanism reveals that a radical pathway is possibly involved.

Key words: selenylated maleimide, selenylated alkene, bromide catalysis, selenylation, radical reaction

Cite this article

Zhouting Zeng, Huaixin Wei, Wei-Min He, Mingming Yu, Zu-Li Wang, Jinhui Cai. Synthesis of Selenylated Maleimides and Alkenes via Bromide Catalysis[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3786-3796.

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Fig. & Tab. 8

Scheme 1. Strategies for the assembly of selenylated maleimides

Entry^a	Bromide salt	Solvent	Yield^b/%
1	KBr	DMSO	57
2	NaBr	DMSO	45
3	NH₄Br	DMSO	91
4	IBr	DMSO	6
5	TBAB	DMSO	17
6	NH₄Br	1,4-Dioxane	0
7	NH₄Br	DMF	0
8	NH₄Br	NMP	0
9	NH₄Br	PhCl	0
10^c	NH₄Br	DMSO	76
11^d	NH₄Br	DMSO	11
12^e	NH₄Br	DMSO	89
13^f	NH₄Br	DMSO	72
14	NH₄I	DMSO	0
15	NH₄F	DMSO	0

Table 1. Optimization of reaction conditionsa

Table 2. Substrate scope of maleimides 1a

Table 3. Substrate scope of boronic acids 3a

Table 4. Substrate scope of boronic acids 3 and 1,1-diaryl- ethylenes 2a,b

Scheme 2. Scale-up reaction and derivatizations of compound 4a

Scheme 3. Mechanistic experiments

Scheme 4. Possible mechanism

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