Copper-Catalyzed C—H Bond and N—H Bond Insertion Reaction Based on Azide-Ynamide Cyclization

doi:10.6023/cjoc202009020

Abstract

A copper-catalyzed azide-ynamide cyclization to synthesize isoquinoline derivatives is reported. First, α-imino copper carbene intermediate is generated via Cu(I)-catalyzed azide-ynamide cyclization, then this copper carbene can be captured by indoles and anilines to form C—H and N—H insertion products. The notable advantages of this method include a simple procedure, mild reaction conditions and widespread availability of the substrates. Thus, this protocol provides a highly convenient and efficient route for the preparation of natural products and active molecules which contain the isoquinoline-indole or isoquinoline-aniline skeletons.

Key words: cyclization reaction, copper catalysis, copper carbenes, ynamides

Cite this article

Xiaotao Liu, Xin Liu, Longwu Ye. Copper-Catalyzed C—H Bond and N—H Bond Insertion Reaction Based on Azide-Ynamide Cyclization[J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1207-1215.

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Entry	Catalyst	Condition	Yield^b/% 3a	Yield^b/% 3a'°
1	Cu(CH₃CN)₄PF₆	DCE, 60 ℃, 2 h	52	35
2	Cu(CH₃CN)₄BF₄	DCE, 60 ℃, 2 h	58	28
3	Cu(OTf)	DCE, 60 ℃, 2.5 h	42	50
4	CuCl	DCE, 60 ℃, 8 h	40	46
5	Cu(CH₃CN)₄BF₄	CHCl₃, 60 ℃, 2 h	57	33
6	Cu(CH₃CN)₄BF₄	Toluene, 60 ℃, 6 h	60	29
7	Cu(CH₃CN)₄BF₄	DCE, 40 ℃, 16 h	64	32
8	Cu(CH₃CN)₄BF₄	DCE, 80 ℃, 1 h	83	<10
9^c	Cu(CH₃CN)₄BF₄	DCE, 80 ℃, 2 h	64	18
10^d	Cu(CH₃CN)₄BF₄	DCE, 80 ℃, 1 h	84	<10

Entry	Catalyst	Condition	Yield^b/% 3a	Yield^b/% 3a'°
1	Cu(CH₃CN)₄PF₆	DCE, 60 ℃, 2 h	52	35
2	Cu(CH₃CN)₄BF₄	DCE, 60 ℃, 2 h	58	28
3	Cu(OTf)	DCE, 60 ℃, 2.5 h	42	50
4	CuCl	DCE, 60 ℃, 8 h	40	46
5	Cu(CH₃CN)₄BF₄	CHCl₃, 60 ℃, 2 h	57	33
6	Cu(CH₃CN)₄BF₄	Toluene, 60 ℃, 6 h	60	29
7	Cu(CH₃CN)₄BF₄	DCE, 40 ℃, 16 h	64	32
8	Cu(CH₃CN)₄BF₄	DCE, 80 ℃, 1 h	83	<10
9^c	Cu(CH₃CN)₄BF₄	DCE, 80 ℃, 2 h	64	18
10^d	Cu(CH₃CN)₄BF₄	DCE, 80 ℃, 1 h	84	<10

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