Silver-Catalyzed Asymmetric Cycloaddition Reaction of Difluoro- methyl Containing Vinyl Indoles and Azodicarboxylates

doi:10.6023/cjoc202601043

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (8): 3255-3267.DOI: 10.6023/cjoc202601043 Previous Articles Next Articles

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银催化二氟甲基取代的乙烯吲哚与偶氮二甲酸酯的不对称环加成反应

唐磊^a^,^b, 赵刚^a^,^b^,^*()

^a 中国科学技术大学化学与材料科学学院合肥 230026
^b 中国科学院上海有机化学研究所先进氟氮材料全国重点实验室上海 200032

收稿日期:2026-01-27 修回日期:2026-04-08 发布日期:2026-04-27
通讯作者: 赵刚
基金资助:
中国科学院战略性先导科技专项(XDB0590000)

Silver-Catalyzed Asymmetric Cycloaddition Reaction of Difluoro- methyl Containing Vinyl Indoles and Azodicarboxylates

Lei Tang^a^,^b, Gang Zhao^a^,^b^,^*()

^a School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026
^b Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2026-01-27 Revised:2026-04-08 Published:2026-04-27
Contact: Gang Zhao
Supported by:
Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0590000)

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Abstract

Based on the catalytic system consisting of a monodentate phosphine ligand and silver salt developed by our group, an asymmetric dearomative annulation of 3-difluoromethyl containing vinyl indoles with azodicarboxylates has been established to afford a series of difluoromethy containing chiral azapolycycles. This method provides an efficient access to chiral difluoromethylated dihydroindole derivatives with high yields, low catalyst loading, and good enantioselectivity.

Key words: silver catalysis, asymmetric dearomative cycloaddition, difluoromethyl, azodicarboxylate

Cite this article

Lei Tang, Gang Zhao. Silver-Catalyzed Asymmetric Cycloaddition Reaction of Difluoro- methyl Containing Vinyl Indoles and Azodicarboxylates[J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 3255-3267.

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Fig. & Tab. 6

Scheme 1. Asymmetric dearomative cycloaddition of 3-viny-lindoles their derivatives

Entry	Ligand	Cat. loading/mol%	Yield^b/%	ee^c/%
1^d	L1	10	NR	ND
2	L2	10	85	68
3	L3	10	87	85
4	L4	10	85	21
5	L5	10	84	31
6	L6	10	78	85
7	L7	10	84	43
8	L8	10	85	71
9	L9	10	85	71
10	L10	10	81	83
11	L11	10	82	84
12	L12	10	84	49
13	L13	10	79	80
14	L14	10	80	73
15	L3	5	84	85
16	L3	2	87	87
17^e	L3	2	75	70

Table 1. Optimization of the reaction conditions

Table 2. Scope of substrates

Scheme 2. Dearomatization reactions of other vinylindole compounds with azodicarboxylates

Scheme 3. Reaction of benzene-substituted difluoromethylenated olefin with DBAD

Scheme 4. Proposed reaction mechanism

References 14

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银催化二氟甲基取代的乙烯吲哚与偶氮二甲酸酯的不对称环加成反应

Silver-Catalyzed Asymmetric Cycloaddition Reaction of Difluoro- methyl Containing Vinyl Indoles and Azodicarboxylates

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