Brønsted Acid-Catalyzed Primary Amination of Allylic Alcohols

doi:10.6023/cjoc202501009

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (8): 2932-2937.DOI: 10.6023/cjoc202501009 Previous Articles Next Articles

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Brønsted酸催化烯丙醇的伯胺化反应

王小燕, 徐长明^*()

兰州交通大学化学化工学院兰州 730070

收稿日期:2025-01-13 修回日期:2025-03-04 发布日期:2025-03-31
基金资助:
国家自然科学基金(22061025); 甘肃省自然科学基金(20JR10RA220); 兰州交通大学“百人计划”资助项目.

Brønsted Acid-Catalyzed Primary Amination of Allylic Alcohols

Xiaoyan Wang, Changming Xu^*()

School of Chemistry and Chemical Engineering, Lanzhou Jiaotong University, Lanzhou 730070

Received:2025-01-13 Revised:2025-03-04 Published:2025-03-31
Contact: *E-mail:xucm@mial.lzjtu.cn
Supported by:
National Natural Science Foundation of China(22061025); Natural Science Foundation of Gansu Province(20JR10RA220); Foundation of a Hundred Youth Talents Training Program of Lanzhou Jiaotong University.

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Abstract

A Brønsted acid-catalyzed primary amination reaction of allylic alcohols with sulfamic acid (NH₃SO₃) is described, giving primary allylic amines with up to 97% yield. The possible reaction mechanism was that allylic alcohol was protonated by Brønsted acid, followed by dehydration led to the formation of allylic carbocation, which reacted with ammonia gas generated in situ to obtain primary allylic amine. This method provides a new approach for synthesizing gram-scale primary allylic amines under mild, transition metal-free and environmentally friendly conditions.

Key words: allylic alcohols, sulfamic acid, primary amination, Brønsted acid

Cite this article

Xiaoyan Wang, Changming Xu. Brønsted Acid-Catalyzed Primary Amination of Allylic Alcohols[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2932-2937.

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Fig. & Tab. 5

References 19

[1]	(a) Petranyi, G.; Ryder, N. S.; Stütz, A. Science 1984, 224, 1239. pmid: 6547247
	(b) Stütz, A. Angew. Chem., Int. Ed. 1987, 26, 320. pmid: 6547247
	(c) Nanavati, S. M.; Silverman, R. B. J. Am. Chem. Soc. 1991, 113, 9341. pmid: 6547247
	(d) Trost, B. M.; Crawley, M. L. Chem. Rev. 2003, 103, 2921. pmid: 6547247
	(e) Hayashi, S.; Yorimitsu, H.; Oshima, K. Angew. Chem., Int. Ed. 2009, 48, 7224. pmid: 6547247
[2]	(a) Takeuchi, R.; Kezuka, S. Synthesis 2006, 3349.
	(b) Lu, Z.; Ma, S.-M. Angew. Chem., Int. Ed. 2008, 47, 258.
[3]	Defieber, C.; Ariger, M. A.; Moriel, P.; Carreira, E. M. Angew. Chem., Int. Ed. 2007, 46, 3139.
[4]	Roggen, M.; Carreira, E. M. J. Am. Chem. Soc. 2010, 132, 11917.
[5]	Lafrance, M.; Roggen, M.; Carreira, E. M. Angew. Chem., Int. Ed. 2012, 51, 3470.
[6]	Zhou, L.-J.; Zanda, N.; Chaudhari, M.; Silva, M. F. D.; Pericàs, M. A. J. Org. Chem. 2023, 88, 2166.
[7]	Nagano, T.; Kobayashi, S. J. Am. Chem. Soc. 2009, 131, 4200.
[8]	Das, K.; Shibuya, R.; Nakahara, Y.; Germain, N.; Ohshima, T.; Mashima, K. Angew. Chem., Int. Ed. 2012, 51, 150.
[9]	Yin, P.; Wong, M. Y.; Tham, J.; Loh, T. P. Org. Chem. Front. 2014, 1, 1266.
[10]	For some selected examples on metal-free allylation and amination, see: (a) Wang, G.-Q.; Gao, L.-Z.; Chen, H.; Liu, X.-T.; Cao, J.; Chen, S.-D.; Cheng, X.; Li, S.-H. Angew. Chem., Int. Ed. 2019, 58, 1694.
	(b) Liu, Z.-L.; Li, G.-H.; Yao, T.-F.; Zhang, J.-L.; Liu, L. Adv. Synth. Catal. 2021, 363, 2740.
	(c) Meng, S.-S.; Tang, X.-W.; Luo, X.; Wu, R.-B.; Zhao, J.-L.; Chan, A. S. C. ACS Catal. 2019, 9, 8397.
[11]	Yan, X.-Y.; Yu, B.-K.; Zhang, H.-C.; Huang, H.-M. J. Org. Chem. 2022, 87, 16918.
[12]	Li, X.-D.; Xie, L.-J.; Kong, D.-L.; Liu, L.; Cheng, L. Tetrahedron 2016, 72, 1873.
[13]	Peng, B.-F.; Ma, J.-G.; Guo, J.-H.; Gong, Y.-T.; Wang, R.-H.; Zhang, Y.; Zeng, J.-L.; Chen, W.-W.; Ding, K.-L.; Zhao, B.-G. J. Am. Chem. Soc. 2022, 144, 2853.
[14]	Xu, W.-L.; Zhou, Y.-G.; Wang, R.-M.; Wu, G.-T.; Chen, P. Org. Biomol. Chem. 2012, 10, 367.
[15]	Tajbakhsh, M.; Lakouraj, M. M.; Shirini, F.; Habibzadeh, S.; Nikdoost, A. Tetrahedron Lett. 2004, 45, 3295.
[16]	Sai, M. Adv. Synth. Catal. 2018, 360, 3482.
[17]	Song, P.; Lu, C.-R.; Fei, Z.-H.; Zhao, B.; Yao, Y.-M. J. Org. Chem. 2018, 83, 6093.
[18]	Chen, G.; Sasaki, M.; Yudin, A. K. Tetrahedron Lett. 2006, 47, 255.
[19]	Li, M.-Y.; Gutierrez, O.; Berritt, S.; Escudero, A. P.; Yesilcimen, A.; Yang, X.-D.; Adrio, J.; Huang, G.; Ogiso, E. N.; Kozlowski, M. C.; Walsh, P. J. Nat. Chem. 2017, 9, 997.

Entry	Catal.	x	Solvent	Temp./℃	Time/h	Yield/%
1	TsOH	5	Tol	80	9	69
2	MsOH	5	Tol	80	8	62
3	TFA	5	Tol	80	8	38
4	TfOH	5	Tol	80	1	90
5	TfOH	5	Tol	r.t.	27	93
6	—	5	Tol	r.t.	48	26
7	TfOH	0	Tol	r.t.	3	Mess
8	TfOH	3	Tol	r.t.	48	72
9	TfOH	10	Tol	r.t.	27	83
10	TfOH	—	DMF	r.t.	24	Trace
11	TfOH	5	THF	r.t.	26	31
12	TfOH	5	1,4-Dioxane	r.t.	26	45
13	TfOH	5	DCE	r.t.	21	38
14	TfOH	5	MeCN	r.t.	6	31
15^c	TfOH	0	Tol	r.t.	24	NR
16^d	TfOH	0	1,4-Dioxane	r.t.	6	NR

Entry	Catal.	x	Solvent	Temp./℃	Time/h	Yield/%
1	TsOH	5	Tol	80	9	69
2	MsOH	5	Tol	80	8	62
3	TFA	5	Tol	80	8	38
4	TfOH	5	Tol	80	1	90
5	TfOH	5	Tol	r.t.	27	93
6	—	5	Tol	r.t.	48	26
7	TfOH	0	Tol	r.t.	3	Mess
8	TfOH	3	Tol	r.t.	48	72
9	TfOH	10	Tol	r.t.	27	83
10	TfOH	—	DMF	r.t.	24	Trace
11	TfOH	5	THF	r.t.	26	31
12	TfOH	5	1,4-Dioxane	r.t.	26	45
13	TfOH	5	DCE	r.t.	21	38
14	TfOH	5	MeCN	r.t.	6	31
15^c	TfOH	0	Tol	r.t.	24	NR
16^d	TfOH	0	1,4-Dioxane	r.t.	6	NR

Brønsted酸催化烯丙醇的伯胺化反应

Brønsted Acid-Catalyzed Primary Amination of Allylic Alcohols

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