铱催化的苯甲酰胺和磷酰叠氮在离子液体中的C—H键胺化反应

doi:10.6023/cjoc202104039

摘要/Abstract

磷酰胺是天然产物和生物活性分子中常见结构, 也是合成化学中重要的中间体. 报道了一种直接、简单、高效且相对绿色的过渡金属铱催化的C—H键胺基化反应, 以弱配位的苯甲酰胺类化合物和磷酰叠氮化合物分别为反应底物和胺基化试剂, 在离子液体中实现了目标转化, 得到中等到优良的分离产率, 表现出良好的官能团耐受性和较高的区域选择性, 并提出了反应的可能机理. 该催化体系的建立丰富了磷酰胺的合成途径, 拓展了离子液体类绿色介质在C—H键官能化中的应用.

关键词: 过渡金属, 离子液体, 碳氢活化, 胺基化, 区域选择性, 磷酰叠氮

Phosphoramides are common structures in natural products and bioactive molecules. Additionally, they are also important intermediates in synthetic chemistry. In this paper, a direct, simple, efficient and relatively greener transition metal iridium catalyzed C—H bond amidation was reported. The target conversion was achieved in ionic liquids using weakly coordinated benzamides and phosphoryl azides as substrates and amidation reagents, respectively. Moderate to excellent isolated yields were obtained, showing good functional group tolerance and high regioselectivity. Furthermore, a possible mechanism of the reaction was proposed. The establishment of the catalytic system enriches the synthesis protocols of phosphoramides and extends the application of ionic liquids as green media in the C—H bond functionalization.

Key words: transition metal, ionic liquids, hydrocarbon activation, amidation, regioselectivity, phosphoryl azid

引用此文

宁资慧, 彭欣华, 白瑞, 刘珊珊, 李卓, 焦林郁. 铱催化的苯甲酰胺和磷酰叠氮在离子液体中的C—H键胺化反应[J]. 有机化学, 2021, 41(11): 4484-4492.

Zihui Ning, Xinhua Peng, Rui Bai, Shanshan Liu, Zhuo Li, Linyu Jiao. Iridium Catalyzed C—H Amidation of Benzamides with Phosphoryl Azides in Ionic Liquids[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4484-4492.

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参考文献 15

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Entry	Catalyst	Silver salt	Additive (50 mol%)	Solvent	T/℃	Yield^b/%
1	[IrCp*Cl₂]₂	AgNTf₂	NaOAc	[BMIM]BF₄	r.t.	ND^c
2	[IrCp*Cl₂]₂	AgNTf₂	NaOAc	[BMIM]BF₄	40	Trace
3	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]BF₄	80	38
4	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]BF₄	100	ND^c
5	[IrCp*Cl₂]₂	AgSbF₆	—	[BMIM]BF₄	80	25
6	[IrCp*Cl₂]₂	AgBF₄	—	[BMIM]BF₄	80	Trace
7	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]PF₆	80	ND^c
8	[IrCp*Cl₂]₂	AgNTf₂	Li₂CO₃	[BMIM]BF₄	80	ND^c
9	[IrCp*Cl₂]₂	AgNTf₂	AgOAc	[BMIM]BF₄	80	82
10	[IrCp*Cl₂]₂	AgNTf₂	Ag₂O	[BMIM]BF₄	80	15
11	[IrCp*Cl₂]₂	AgNTf₂	Ag₂CO₃	[BMIM]BF₄	80	Trace
12	[IrCp*Cl₂]₂	AgNTf₂	TFA	[BMIM]BF₄	80	ND^c
13	[IrCp*Cl₂]₂	AgNTf₂	AgOAc	[BMIM]PF₆	80	Trace
14	[RhCp*Cl₂]₂	AgSbF₆	—	[BMIM]PF₆	80	ND^c
15	[RhCp*Cl₂]₂	AgSbF₆	NaOAc	[BMIM]PF₆	80	ND^c
16	[RhCp*Cl₂]₂	—	Li₂CO₃	[BMIM]BF₄	80	ND^c

Entry	Catalyst	Silver salt	Additive (50 mol%)	Solvent	T/℃	Yield^b/%
1	[IrCp*Cl₂]₂	AgNTf₂	NaOAc	[BMIM]BF₄	r.t.	ND^c
2	[IrCp*Cl₂]₂	AgNTf₂	NaOAc	[BMIM]BF₄	40	Trace
3	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]BF₄	80	38
4	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]BF₄	100	ND^c
5	[IrCp*Cl₂]₂	AgSbF₆	—	[BMIM]BF₄	80	25
6	[IrCp*Cl₂]₂	AgBF₄	—	[BMIM]BF₄	80	Trace
7	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]PF₆	80	ND^c
8	[IrCp*Cl₂]₂	AgNTf₂	Li₂CO₃	[BMIM]BF₄	80	ND^c
9	[IrCp*Cl₂]₂	AgNTf₂	AgOAc	[BMIM]BF₄	80	82
10	[IrCp*Cl₂]₂	AgNTf₂	Ag₂O	[BMIM]BF₄	80	15
11	[IrCp*Cl₂]₂	AgNTf₂	Ag₂CO₃	[BMIM]BF₄	80	Trace
12	[IrCp*Cl₂]₂	AgNTf₂	TFA	[BMIM]BF₄	80	ND^c
13	[IrCp*Cl₂]₂	AgNTf₂	AgOAc	[BMIM]PF₆	80	Trace
14	[RhCp*Cl₂]₂	AgSbF₆	—	[BMIM]PF₆	80	ND^c
15	[RhCp*Cl₂]₂	AgSbF₆	NaOAc	[BMIM]PF₆	80	ND^c
16	[RhCp*Cl₂]₂	—	Li₂CO₃	[BMIM]BF₄	80	ND^c

Entry	R¹	R²	Product	t/h	Yield^b/%
1	H	Me	5aa	24	66
2	H	n-Pr	5ba	24	56
3	H	i-Pr	5ca	24	50
4	H	Cy	5da	24	48
5	i-Pr	i-Pr	5ea	30	ND^c

Entry	R¹	R²	Product	t/h	Yield^b/%
1	H	Me	5aa	24	66
2	H	n-Pr	5ba	24	56
3	H	i-Pr	5ca	24	50
4	H	Cy	5da	24	48
5	i-Pr	i-Pr	5ea	30	ND^c

Entry	R (1)	Product	t/h	Yield^b/%
1	H (1a)	3aa	24	82
2	3-Me (1b)	3ba	24	56
3	4-Me (1c)	3ca	24	55
4	4-OMe (1d)	3da	36	58
5	4-F (1e)	3ea	24	67
6	4-Cl (1f)	3fa	30	65
7	4-Br (1g)	3ga	30	56
8	4-NO₂ (1h)	3ha	30	73