Ruthenium Complex-Catalyzed Tandem Reactions of Alcohols with Acetonitriles for Synthesis of α-Substituted Amides

doi:10.6023/cjoc202204039

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (8): 2418-2427.DOI: 10.6023/cjoc202204039 Previous Articles Next Articles

ARTICLES

金属钌配合物催化醇与腈串联反应合成α-取代酰胺

王梅, 龚慧华, 付海燕, 郑学丽, 陈华, 李瑞祥^*()

四川大学化学学院成都 610064

收稿日期:2022-04-15 修回日期:2022-05-24 发布日期:2022-05-27
通讯作者: 李瑞祥
基金资助:
国家自然科学基金(21572137)

Ruthenium Complex-Catalyzed Tandem Reactions of Alcohols with Acetonitriles for Synthesis of α-Substituted Amides

Mei Wang, Huihua Gong, Haiyan Fu, Xueli Zheng, Hua Chen, Ruixiang Li()

College of Chemistry, Sichuan University, Chengdu 641400

Received:2022-04-15 Revised:2022-05-24 Published:2022-05-27
Contact: Ruixiang Li
Supported by:
National Natural Science Foundation of China(21572137)

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Abstract

A ruthenium complex-catalyzed tandem reaction of alcohols with nitriles in one pot has been developed, providing a green and atom-economic synthetic method of α-substituted amide. This method features high reactivity, high selectivity and good substrate compatibility. Good to high yields are obtained for most substrates and the highest yield is 96%. Mechanistic studies reveal that the alcohol first undergoes an acceptorless dehydrogenation into aldehyde. the resulting aldehyde occurs a nucleophilic addition with the α-position carbon of phenylacetonitrile to form α,β-unsaturated nitrile and water. Subsequently, the unsaturated nitrile is hydrogenated with ruthenium-hydride species formed by the dehydrogenation of alcohol to give saturated nitrile, and then the water, generated by the nucleophilic addition, causes the catalytic hydrolysis of cyano group to finally generate α-arylamide.

Key words: ruthenium complex, alcohol, nitrile, α-arylamide

Cite this article

Mei Wang, Huihua Gong, Haiyan Fu, Xueli Zheng, Hua Chen, Ruixiang Li. Ruthenium Complex-Catalyzed Tandem Reactions of Alcohols with Acetonitriles for Synthesis of α-Substituted Amides[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2418-2427.

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References 28

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Entry	Cat.	Base (equiv.)	Temp./℃	Solvent	Yield/%
1	Ru-PPh₃	KO^tBu (1)	120	Toluene	18
2	Ru-CNN	KO^tBu (1)	120	Toluene	46
3	Ru-CNP	KO^tBu (1)	120	Toluene	33
4	Ru-CNN	K₂CO₃(1)	120	Toluene	Trace
5	Ru-CNN	KOH (1)	120	Toluene	23
6	Ru-CNN	KOMe (1)	120	Toluene	37
7	Ru-CNN	KO^tBu (1)	110	Toluene	49
8	Ru-CNN	KO^tBu (1)	100	Toluene	58
9	Ru-CNN	KO^tBu (1)	90	Toluene	73
10	Ru-CNN	KO^tBu (1)	80	Toluene	64
11	Ru-CNN	KO^tBu (0.5)	90	Toluene	38
12	Ru-CNN	KO^tBu (2)	90	Toluene	90
13	Ru-CNN	KO^tBu (3)	90	Toluene	72
14	Ru-CNN	KO^tBu (2)	90	DMSO	—
15	Ru-CNN	KO^tBu (2)	90	Acetonitrile	14
16	Ru-CNN	KO^tBu (2)	90	1,4-Dioxane	59
17	—	KO^tBu (2)	90	Toluene	—
18	Ru-CNN	—	90	Toluene	—

Entry	Cat.	Base (equiv.)	Temp./℃	Solvent	Yield/%
1	Ru-PPh₃	KO^tBu (1)	120	Toluene	18
2	Ru-CNN	KO^tBu (1)	120	Toluene	46
3	Ru-CNP	KO^tBu (1)	120	Toluene	33
4	Ru-CNN	K₂CO₃(1)	120	Toluene	Trace
5	Ru-CNN	KOH (1)	120	Toluene	23
6	Ru-CNN	KOMe (1)	120	Toluene	37
7	Ru-CNN	KO^tBu (1)	110	Toluene	49
8	Ru-CNN	KO^tBu (1)	100	Toluene	58
9	Ru-CNN	KO^tBu (1)	90	Toluene	73
10	Ru-CNN	KO^tBu (1)	80	Toluene	64
11	Ru-CNN	KO^tBu (0.5)	90	Toluene	38
12	Ru-CNN	KO^tBu (2)	90	Toluene	90
13	Ru-CNN	KO^tBu (3)	90	Toluene	72
14	Ru-CNN	KO^tBu (2)	90	DMSO	—
15	Ru-CNN	KO^tBu (2)	90	Acetonitrile	14
16	Ru-CNN	KO^tBu (2)	90	1,4-Dioxane	59
17	—	KO^tBu (2)	90	Toluene	—
18	Ru-CNN	—	90	Toluene	—

金属钌配合物催化醇与腈串联反应合成α-取代酰胺

Ruthenium Complex-Catalyzed Tandem Reactions of Alcohols with Acetonitriles for Synthesis of α-Substituted Amides

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