苯炔与邻芳基甲酰苯乙腈串联反应合成9-氰基蒽衍生物

doi:10.6023/cjoc202503005

摘要/Abstract

介绍了一种在温和条件下, 利用苯炔与邻芳基甲酰苯乙腈串联反应构建9-氰基蒽衍生物的新方法. 以2-(三甲基硅)苯基三氟甲烷磺酸酯为苯炔前体, 以KF/18-C-6为氟源, ^tBuONa为碱, 原位生成的苯炔与邻芳基甲酰苯乙腈发生碳亲核进攻引发的串联环化/芳构化反应, 以47%~95%的产率合成了20种不同取代基团的9-氰基蒽衍生物.

关键词: 苯炔, 邻芳基甲酰苯乙腈, 9-氰基蒽

A new method for constructing 9-cyanoanthracene compounds by reacting aryne with ortho-arylformylphenyl-acetonitrile under mild conditions was introduced. Using 2-(trimethylsilicone)phenyltrifluoromethanesulfonate as the aryne precursor, KF/18-C-6 as the fluorine source, and ^tBuONa as the base, the aryne in situ generated can undergo a tandem cyclization/aromatization reaction triggered by carbon nucleophilic attack with ortho-arylformylphenylacetonitrile, and 20 differently substituted 9-cyanoanthracene products were synthesized in 47%~95% yields.

Key words: aryne, ortho-arylformylphenylacetonitrile, 9-cyanoanthracene

引用此文

李双俊, 龚潩, 张放, 杜广芬, 何林. 苯炔与邻芳基甲酰苯乙腈串联反应合成9-氰基蒽衍生物[J]. 有机化学, 2025, 45(10): 3816-3823.

Shuangjun Li, Yi Gong, Fang Zhang, Guangfen Du, Lin He. Synthesis of 9-Cyanoanthracene Derivatives by Tandem Reaction of Aryne with ortho-Arylformylphenylacetonitrile[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3816-3823.

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Entry	Fluoride source	Base	Additive	Solvent	Yield^b/%
1	KF/18-C-6			THF	16
2	KF/18-C-6	Cs₂CO₃		THF	34
3	CsF	Cs₂CO₃		THF	12
4	CsF/18-C-6	Cs₂CO₃		THF	17
5	TBAF•3H₂O	Cs₂CO₃		THF	44
6	TMAF•4H₂O	Cs₂CO₃		THF	40
7	TBAF•3H₂O	Cs₂CO₃	4 Å MS	THF	65
8	TMAF•4H₂O	Cs₂CO₃	4 Å MS	THF	58
9	KF/18-C-6	Cs₂CO₃	4 Å MS	THF	69
10	KF/18-C-6	K₂CO₃	4 Å MS	THF	41
11	KF/18-C-6	^tBuOK	4 Å MS	THF	68
12	KF/18-C-6	^tBuONa	4 Å MS	THF	88
13	KF/18-C-6	^tBuONa	4 Å MS	DME	47
14	KF/18-C-6	^tBuONa	4 Å MS	Toluene	59
15	KF/18-C-6	^tBuONa	4 Å MS	DCM	21
16	KF/18-C-6	^tBuONa	4 Å MS	CH₃CN	28
17^c	KF/18-C-6	^tBuONa	4 Å MS	THF	53
18^d	KF/18-C-6	^tBuONa	4 Å MS	THF	40
19^e	KF/18-C-6	^tBuONa	4 Å MS	THF	50
20^f	KF/18-C-6	^tBuONa	4 Å MS	THF	61
21^g	KF/18-C-6	^tBuONa	4 Å MS	THF	64
22^h	KF/18-C-6	^tBuONa	4 Å MS	THF	49
23ⁱ	KF/18-C-6	^tBuONa	4 Å MS	THF	36

Entry	Fluoride source	Base	Additive	Solvent	Yield^b/%
1	KF/18-C-6			THF	16
2	KF/18-C-6	Cs₂CO₃		THF	34
3	CsF	Cs₂CO₃		THF	12
4	CsF/18-C-6	Cs₂CO₃		THF	17
5	TBAF•3H₂O	Cs₂CO₃		THF	44
6	TMAF•4H₂O	Cs₂CO₃		THF	40
7	TBAF•3H₂O	Cs₂CO₃	4 Å MS	THF	65
8	TMAF•4H₂O	Cs₂CO₃	4 Å MS	THF	58
9	KF/18-C-6	Cs₂CO₃	4 Å MS	THF	69
10	KF/18-C-6	K₂CO₃	4 Å MS	THF	41
11	KF/18-C-6	^tBuOK	4 Å MS	THF	68
12	KF/18-C-6	^tBuONa	4 Å MS	THF	88
13	KF/18-C-6	^tBuONa	4 Å MS	DME	47
14	KF/18-C-6	^tBuONa	4 Å MS	Toluene	59
15	KF/18-C-6	^tBuONa	4 Å MS	DCM	21
16	KF/18-C-6	^tBuONa	4 Å MS	CH₃CN	28
17^c	KF/18-C-6	^tBuONa	4 Å MS	THF	53
18^d	KF/18-C-6	^tBuONa	4 Å MS	THF	40
19^e	KF/18-C-6	^tBuONa	4 Å MS	THF	50
20^f	KF/18-C-6	^tBuONa	4 Å MS	THF	61
21^g	KF/18-C-6	^tBuONa	4 Å MS	THF	64
22^h	KF/18-C-6	^tBuONa	4 Å MS	THF	49
23ⁱ	KF/18-C-6	^tBuONa	4 Å MS	THF	36