Ag/Cu-Mediated Decarboxylative Cyanation of Arene Carboxylic Acids Using NH4 +/N,N-Dimethylformamide as Combined Cyanide Source

doi:10.6023/cjoc202006031

Abstract

A Ag/Cu-mediated decarboxylative cyanation of aryl carboxylic acids has been well established using NH₄OAc/ N, N-dimethylformamide (DMF) as a combined cyanide source under aerobic conditions, and the synthesis of perampanel was further realized with this method as the key step. Preliminary mechanistic investigation indicated the “CN” of desired products was from the combination of DMF and ammonium salt. Cu in the catalytic system was essential for the process, whereas Ag was beneficial for the transformation.

Key words: decarboxylation, aryl nitrile, aerobic conditions

Cite this article

Zhengjiang Fu, Guangguo Hao, Quanqing Shi,, Jinqi Zhou, Ligao Jiang, Shuiliang Wang, Shengmei Guo, Hu Cai. Ag/Cu-Mediated Decarboxylative Cyanation of Arene Carboxylic Acids Using NH₄ ⁺/N,N-Dimethylformamide as Combined Cyanide Source[J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 333-340.

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Entry	[Ag] (equiv.)	[Cu] (equiv.)	“N” (equiv.)	Additive (equiv.)	Yield ^b /%
1	Ag ₂SO ₄ (0.1)	Cu(OAc) ₂ (1)	Ethylenediamine (1.5)	—	40
2	Ag ₂SO ₄(0.1)	Cu(OAc) ₂ (1)	NH ₄OAc (3)	—	43
3	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1)	NH ₄OAc (3)	—	46
4	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1)	NH ₄OAc (3)	EtCOOH (2)	55
5	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂(1)	NH ₄OAc (3)	MeCOOH (2)	52
6	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	79
7	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	PhCOOH (2)	63
8	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	^t BuCOOH (2)	40
9	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	AdCOOH (2)	61
10	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₃•H ₂O (3)	EtCOOH (2)	55
11	Ag ₂SO ₄ (0.05)	Cu(TFA) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	40
12	Ag ₂SO ₄ (0.05)	CuI (1.6)	NH ₄OAc (3)	EtCOOH (2)	36
13	Ag ₂O (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	42
14	Ag ₂CO ₃ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	54
15	AgOTf (0.1)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	51
16 ^c	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	43
17 ^d	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	10
18 ^e	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	38

Entry	[Ag] (equiv.)	[Cu] (equiv.)	“N” (equiv.)	Additive (equiv.)	Yield ^b /%
1	Ag ₂SO ₄ (0.1)	Cu(OAc) ₂ (1)	Ethylenediamine (1.5)	—	40
2	Ag ₂SO ₄(0.1)	Cu(OAc) ₂ (1)	NH ₄OAc (3)	—	43
3	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1)	NH ₄OAc (3)	—	46
4	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1)	NH ₄OAc (3)	EtCOOH (2)	55
5	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂(1)	NH ₄OAc (3)	MeCOOH (2)	52
6	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	79
7	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	PhCOOH (2)	63
8	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	^t BuCOOH (2)	40
9	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	AdCOOH (2)	61
10	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₃•H ₂O (3)	EtCOOH (2)	55
11	Ag ₂SO ₄ (0.05)	Cu(TFA) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	40
12	Ag ₂SO ₄ (0.05)	CuI (1.6)	NH ₄OAc (3)	EtCOOH (2)	36
13	Ag ₂O (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	42
14	Ag ₂CO ₃ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	54
15	AgOTf (0.1)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	51
16 ^c	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	43
17 ^d	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	10
18 ^e	Ag ₂SO ₄ (0.05)	Cu(OAc) ₂ (1.6)	NH ₄OAc (3)	EtCOOH (2)	38

Entry	Change of standard conditions	Isolated yield/%
1	None [Entry 6, Table 1]	79
2	No Ag/Cu	0
3	No Ag	31
4	No Cu	0
5	3 equiv. ¹⁵NH ₄OAc [instead of NH ₄OAc]	75
6	NH ₄I [instead of NH ₄OAc]	43
7	CuI [instead of Cu(OAc) ₂]	36
8	Absence of EtCOOH	56
9	Formamide HCONH ₂ [instead of DMF]	0
10	N, N-Diethylformamide HCONEt ₂ [instead of DMF]	28
11	2 equiv. TEMPO was added as a radical scavenger	15
12	2 equiv. BHT was added as a radical scavenger	12

Entry	Change of standard conditions	Isolated yield/%
1	None [Entry 6, Table 1]	79
2	No Ag/Cu	0
3	No Ag	31
4	No Cu	0
5	3 equiv. ¹⁵NH ₄OAc [instead of NH ₄OAc]	75
6	NH ₄I [instead of NH ₄OAc]	43
7	CuI [instead of Cu(OAc) ₂]	36
8	Absence of EtCOOH	56
9	Formamide HCONH ₂ [instead of DMF]	0
10	N, N-Diethylformamide HCONEt ₂ [instead of DMF]	28
11	2 equiv. TEMPO was added as a radical scavenger	15
12	2 equiv. BHT was added as a radical scavenger	12

以NH₄ ⁺/ N, N-二甲基甲酰胺组合为氰源Ag/Cu介导芳基羧酸的脱羧氰化反应

Ag/Cu-Mediated Decarboxylative Cyanation of Arene Carboxylic Acids Using NH₄ ⁺/N,N-Dimethylformamide as Combined Cyanide Source

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Entry	Yield ^b /%	Entry	Yield ^b /%
1	79	7	35
2	32	8	18
3	64	9	30
4	74	10	0
5	57	11	0
6	37

Entry	Yield ^b /%	Entry	Yield ^b /%
1	79	7	35
2	32	8	18
3	64	9	30
4	74	10	0
5	57	11	0
6	37

以NH4 +/ N, N-二甲基甲酰胺组合为氰源Ag/Cu介导芳基羧酸的脱羧氰化反应