Metal-Free Formation of 2-Substitued Benzoxazoles with Amides and Esters

doi:10.6023/cjoc202111031

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (6): 1778-1785.DOI: 10.6023/cjoc202111031 Previous Articles Next Articles

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无金属条件下酰胺和酯参与的2-取代苯并噁唑衍生物的合成

李芳绍, 肖晶^*(), 吴小芳, 王晓熠, 邓金凤, 唐子龙^*()

湖南科技大学化学化工学院理论有机化学与功能分子教育部重点实验室湖南湘潭 411201

收稿日期:2021-11-22 修回日期:2022-02-08 发布日期:2022-02-25
通讯作者: 肖晶, 唐子龙
基金资助:
国家自然科学基金(21703061); 湖南省科技创新计划(2021RC5028)

Metal-Free Formation of 2-Substitued Benzoxazoles with Amides and Esters

Fangshao Li, Jing Xiao(), Xiaofang Wu, Xiaoyi Wang, Jinfeng Deng, Zilong Tang()

Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201

Received:2021-11-22 Revised:2022-02-08 Published:2022-02-25
Contact: Jing Xiao, Zilong Tang
Supported by:
National Natural Science Foundation of China(21703061); Science and Technology Innovation Program of Hunan Province(2021RC5028)

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Abstract

2-Substituted benzoxazoles are important heterocyclic motifs due to their wide application in pharmacology. A PCl₃-mediated C(2)-functionalization of benzoxazole derivatives with inert amides and esters under metal-free conditions was reported. By using PCl₃/I₂ combination, various 2-substituted benzoxazoles could be synthesized via the arylation or alkylation of benzoxazoles with amides and esters in the presence of water. What’s more, the reactivity between amides and esters was also investigated. The primary results indicated that amides have higher reactivity than esters under this system. This method features a broad substrate scope, simple condition and low-cost. A plausible mechanism was also proposed.

Key words: 2-substituted benzoxazoles, amide, ester, metal-free, phosphorus trichloride

Cite this article

Fangshao Li, Jing Xiao, Xiaofang Wu, Xiaoyi Wang, Jinfeng Deng, Zilong Tang. Metal-Free Formation of 2-Substitued Benzoxazoles with Amides and Esters[J]. Chinese Journal of Organic Chemistry, 2022, 42(6): 1778-1785.

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Fig. & Tab. 9

Scheme 1. Synthesis of 2-substituted benzoxazoles under transition-metal-free conditions.

Entry	PCl₃/equiv.	V(H₂O)/μL	Solvent	Yield^b/%
1	1.2	50	DCE	52
2	1.0	50	DCE	82
3	0.8	50	DCE	70
4	1.0	65	DCE	49
5	1.0	35	DCE	46
6	1.0	0	DCE	0
7	1.0	50	CH₃CN	54
8	1.0	50	Toluene	65
9	1.0	50	PhCl	60
10	1.0	50	DMF	Trace
11	1.0	50	DCE	62^c
12	1.0	50	DCE	21^d
13	1.0	50	DCE	66^e
14	0	50	DCE	0
15	1.0	50	DCE	43^f

Table 1. Optimization of the model reaction conditions

Table 2. C(2) functionalization of benzoxazoles with amides

Table 3. C(2) Functionalization of benzoxazoles with esters

Table 4. Studies on the reactivity of different amides and esters

Table 5. Studies on the reactivity of substrates containing both ester and amide groups

Scheme 2. Scale-up reactions of benzoxazole with N,N-dimethylbenzamide and methyl benzoate

Scheme 3. Exploration of reaction mechanism

Scheme 4. Possible mechanism for the reaction of benzoxazoles with amides or esters

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无金属条件下酰胺和酯参与的2-取代苯并噁唑衍生物的合成

Metal-Free Formation of 2-Substitued Benzoxazoles with Amides and Esters

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