Efficient Synthesis of Nitrile Compounds through Amide Conversion via N-Boroamide Intermediates

doi:10.6023/cjoc202307020

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (2): 638-643.DOI: 10.6023/cjoc202307020 Previous Articles Next Articles

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经由N-硼基酰胺中间体的酰胺高效转化合成腈类化合物

李洋^a^,^b, 董亚楠^a, 李跃辉^a^,^*()

a 中国科学院兰州化学物理研究所苏州实验室羰基合成与选择氧化国家重点实验室兰州 730000
b 中国科学院大学北京 100049

收稿日期:2023-07-20 修回日期:2023-09-22 发布日期:2023-10-12
基金资助:
国家自然科学基金(22022204); 国家自然科学基金(21633013); 国家自然科学基金(22072167); 国家自然科学基金(22202218)

Efficient Synthesis of Nitrile Compounds through Amide Conversion via N-Boroamide Intermediates

Yang Li^a^,^b, Yanan Dong^a, Yuehui Li^a()

a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Laboratory, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000
b University of Chinese Academy of Sciences, Beijing 100049

Received:2023-07-20 Revised:2023-09-22 Published:2023-10-12
Contact: * E-mail: yhli@licp.cas.cn
Supported by:
National Natural Science Foundation of China(22022204); National Natural Science Foundation of China(21633013); National Natural Science Foundation of China(22072167); National Natural Science Foundation of China(22202218)

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Abstract

HBpin is used as a boronizing reagent and formal dehydrating agent is reported for the first time. CsF was used as a catalyst to achieve the dehydration and conversion of primary amides, and various nitrile compounds were obtained with good to excellent yields. This method is easy to operate, and the yield of the target product in the gram scale amplification experiment is 96%. The catalytic system exhibits good compatibility with various functional groups, such as halogen, trifluoromethyl, heterocycle, and amino group. These results indicate that this method has good application potential. Mechanism studies have shown that the in-situ generation of N-boroamide intermediates and H₂ is the key to the smooth occurrence of the reaction. And, the formation of thermodynamically stable B-O-B anhydride and nitrile product is the driving force of this transformation.

Key words: CsF, catalysis, primary amide, cyanation, borane

Cite this article

Yang Li, Yanan Dong, Yuehui Li. Efficient Synthesis of Nitrile Compounds through Amide Conversion via N-Boroamide Intermediates[J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 638-643.

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Entry	Catalyst	[B] (equiv.)	Yield^b/%
1	—	HBpin (2.5)	17
2	Cs₂CO₃	HBpin (2.5)	45
3	CsF	HBpin (2.5)	>99
4	KF	HBpin (2.5)	41
5	^tBuOK	HBpin (2.5)	27
6	CsF	HBpin (2)	81
7	CsF	HBpin (1.5)	31
8	CsF	HBpin (1)	14
9^c	CsF	HBpin (2.5)	71
10^d	CsF	HBpin (2.5)	88
11	CsF	B₂pin₂ (2.5)	Trace
12	CsF	NaBH₄ (2.5)	Trace
13	CsF	NH₃BH₃ (2.5)	34
14^e	CsF	HBpin (2.5)	89
15^f	CsF	HBpin (2.5)	83
16^g	CsF	HBpin (2.5)	76

Entry	Catalyst	[B] (equiv.)	Yield^b/%
1	—	HBpin (2.5)	17
2	Cs₂CO₃	HBpin (2.5)	45
3	CsF	HBpin (2.5)	>99
4	KF	HBpin (2.5)	41
5	^tBuOK	HBpin (2.5)	27
6	CsF	HBpin (2)	81
7	CsF	HBpin (1.5)	31
8	CsF	HBpin (1)	14
9^c	CsF	HBpin (2.5)	71
10^d	CsF	HBpin (2.5)	88
11	CsF	B₂pin₂ (2.5)	Trace
12	CsF	NaBH₄ (2.5)	Trace
13	CsF	NH₃BH₃ (2.5)	34
14^e	CsF	HBpin (2.5)	89
15^f	CsF	HBpin (2.5)	83
16^g	CsF	HBpin (2.5)	76

经由N-硼基酰胺中间体的酰胺高效转化合成腈类化合物

Efficient Synthesis of Nitrile Compounds through Amide Conversion via N-Boroamide Intermediates

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