Polyselenide-Catalyzed Cyclohexene Oxidation to Produce 1,2-Cyclohexanediol

doi:10.6023/cjoc202008032

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (4): 1639-1645.DOI: 10.6023/cjoc202008032 Previous Articles Next Articles

ARTICLES

聚硒醚催化环己烯氧化制备1,2-环己二醇

黄杰军^a^,^c, 钱蓉蓉^b, 王爽^a, 曹洪恩^a^,^*()

a 扬州大学园艺与植物保护学院江苏扬州 225009
b 江苏旅游职业学院江苏扬州 225127
c 江苏扬农化工集团有限公司江苏扬州 225009

收稿日期:2020-08-18 修回日期:2020-09-26 发布日期:2020-12-19
通讯作者: 曹洪恩
基金资助:
国家重点研发计划(2018YFD0200100); 江苏省高校优势学科建设工程资助项目

Polyselenide-Catalyzed Cyclohexene Oxidation to Produce 1,2-Cyclohexanediol

Jiejun Huang^a^,^c, Rongrong Qian^b, Shuang Wang^a, Hong'en Cao^a^,^*()

a School of Horticulture and Plant Protection, Yangzhou University, Yangzhou, Jiangsu 225009
b Jiangsu College of Tourism, Yangzhou, Jiangsu 225127
c Jiangsu Yangnong Chemical Group Co. Ltd, Yangzhou, Jiangsu 225009

Received:2020-08-18 Revised:2020-09-26 Published:2020-12-19
Contact: Hong'en Cao
About author:
* Corresponding author. E-mail: hecao@yzu.edu.cn
Supported by:
National Key Research and Development Program of China(2018YFD0200100); Priority Academic Program Development of Jiangsu Higher Education Institutions

1. cjoc202008032辅助材料.pdf(563KB)

Abstract

A new method for one-step synthesis of polyselenide was developed. The material was found to be an efficient and recyclable catalyst for the dihydroxylation of cyclohexene to produce 1,2-cyclohexanediol, which was an important inter- mediate for the synthesis of many fine chemicals. Interestingly, the unique structure of the catalyst at molecular level resulted in a novel free-radical reaction methanism allowing the utilization of O₂ as the supplementary oxidant, which was quite different from most of the reported organoselenium-catalyzed reactions.

Key words: selenium, polyselenide, cyclohexene, 1,2-cyclohexanediol, green oxidation

Cite this article

Jiejun Huang, Rongrong Qian, Shuang Wang, Hong'en Cao. Polyselenide-Catalyzed Cyclohexene Oxidation to Produce 1,2-Cyclohexanediol[J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1639-1645.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 8

Scheme 1. Synthesis of the polystyrene-supported selenic acid catalyst for cyclohexene dihydroxylation

Figure 1. (a) Preparation steps and (b) element mapping of the polyselenide being synthesized from 1,4-bis(chloromethyl)ben- zene

Entry	Oxidant/Additive	Conversion/%^c	Yield/%^d
1	90 mol% H₂O₂, O₂/—	88	86
2	O₂/—	6	5
3	O₂/200 mol% H₂O	17	16
4	80 mol% H₂O₂, O₂/—	77	76
5	90 mol% H₂O₂, O₂/—	80	79
6	90 mol% H₂O₂, O₂/—	72	70
7	90 mol% H₂O₂, O₂/—	76	74

Table 1. Parallel experiments of the polyselenide-catalyzed dihydroxylation reactions of cyclohexenea

Figure 2. Catalyst recycle and reuse (a) and the SEM images of the polyselenide before (b) and after (c) the 5th cycle of reaction

Entry	Ref.	Consumed weight of starting ma- terials vs. product/(mg?mmol^–1)
1	[14]	493.0
2	[16]	149.8
3	This work	142.9

Table 2. Comparison of the work with reported references on atom economy

Entry	Oxidant/additve	t/h	Conversion/%	Yield^c/%
1	90 mol% H₂O₂, O₂/ TEMPO (100 mol%)	48	0	0
2	90 mol% H₂O₂, O₂/Hy- droquinone (100 mol%)	48	0	0
3	90 mol% H₂O₂, O₂/ AIBN (100 mol%)	24	88	78
4	90 mol% H₂O₂, O₂	24	67	66
5	100 mol% H₂O₂, N₂	48	81	79
6	N₂/200 mol% H₂O^d	48	42	38

Table 3. Control experiments for mechanism studya,b

Figure 3. (a) XPS spectrum of the used catalyst, (b) IR spectra of the polyselenide before and after the reaction and (c) hydroxyl radical capture by salicylic acid via UV-Vis detection

Scheme 2. Plausible mechanism of the Se-polymer-catalyzed oxidation of cyclohexene

References 25

[1]	(a) Chen, Y.; Deng, X.; Jing, X.; Zhou, H. Chin. J. Org. Chem. 2020, 40,4147. (in Chinese) pmid: 29611704
	( 陈颖, 邓鑫, 景崤壁, 周宏伟, 有机化学,2020, 40,4147.) pmid: 29611704
	(b) Ge, Y.; Kong, J.; Yang, C.; Yang, Q.; Zhang, X. Chin. J. Org. Chem. 2020, 40,1760. (in Chinese) pmid: 29611704
	( 葛颜玉, 孔晶, 杨成根, 杨倩, 张旭, 有机化学,2020, 40,1760.) pmid: 29611704
	(c) Bao, W.-H.; He, M.; Wang, J.-T.; Peng, X.; Sung, M.; Tang, Z.; Jiang, S.; Cao, Z.; He, W.-M. J. Org. Chem. 2019, 84,6065. doi: 10.1021/acs.joc.9b00178 pmid: 29611704
	(d) Lu, L.-H.; Wang, Z.; Xia, W.; Cheng, P.; Zhang, B.; Cao, Z.; He, W.-M. Chin. Chem. Lett. 2019, 30,1237. pmid: 29611704
	(e) Higashimae, S.; Kurata, D.; Kawaguchi, S.-I.; Kodama, S.; Sonoda, M.; Nomoto, A.; Ogawa, A. J. Org. Chem. 2018, 83,5267. doi: 10.1021/acs.joc.8b00052 pmid: 29611704
[2]	(a) Ruberte, A.C.; Sanmartin, C.; Aydillo, C.; Sharma, A.K.; Plano, D. J. Med. Chem. 2020, 63,1473. doi: 10.1021/acs.jmedchem.9b01152 pmid: 31638805
	(b) Cao, H.; Yang, Y.; Chen, X.; Liu, J.; Chen, C.; Yuan, S.; Yu, L. Chin. Chem. Lett. 2020, 31,1887. pmid: 31638805
	(c) Mao, X.; Li, P.; Li, T.; Zhao, M.; Chen, C.; Liu, J.; Wang, Z.; Yu, L. Chin. Chem. Lett. 2020, 31,3276. pmid: 31638805
[3]	(a) Wu, C.; Xiao, H.-J.; Wang, S.-W.; Tang, M.-S.; Tang, Z.-L.; Xia, W.; Li, W.-F.; Cao, Z.; He, W.-M. ACS Sustainable Chem. Eng. 2019, 7,2169. pmid: 31588752
	(b) Goulart, T.A. C.; Kazmirski, J.A. G.; Back, D.F.; Zeni, G. J. Org. Chem. 2019, 84,14113. doi: 10.1021/acs.joc.9b02276 pmid: 31588752
	(c) Liu, M.-X.; Li, Y.-M.; Yu, L.; Xu, Q.; Jiang, X.-F. Sci. China: Chem. 2018, 61,294. pmid: 31588752
[4]	(a) Chen, X.; Mao, J.; Liu, C.; Chen, C.; Cao, H.; Yu, L. Chin. Chem. Lett. 2020, 31,3205.
	(b) Zhu, Z.; Wang, W.; Zeng, L.; Zhang, F.; Liu, J. Catal. Commun. 2020, 142,106031.
	(c) Cao, K.-H.; Deng, X.; Chen, T.; Zhang, Q.-T.; Yu, L. J. Mater. Chem. A 2019, 7,10918.
[5]	Singh, F.V.; Wirth, T. Catal. Sci. Technol. 2019, 9,1073.
[6]	(a) Yu, L.; Cao, H.-E.; Zhang, X.; Chen, Y.; Yu, L. Sustainable Energy Fuels 2020, 4,730. pmid: 29583000
	(b) Zheng, Y.-H.; Wu, A.-Q.; Ke, Y.-Y.; Cao, H.-E.; Yu, L. Chin. Chem. Lett. 2019, 30,937. pmid: 29583000
	(c) Liu, X.; Liang, Y.-Y.; Ji, J.-Y.; Luo, J.; Zhao, X.-D. J. Am. Chem. Soc. 2018, 140,4782. doi: 10.1021/jacs.8b01513 pmid: 29583000
	(d) Depken, C.; Krätzschmar, F.; Rieger, R.; Rode, K.; Breder, A. Angew. Chem., Int. Ed. 2018, 57,2459. pmid: 29583000
	(e) Yu, L.; Chen, C. CN 106432739,2017. pmid: 29583000
[7]	Chen, C.; Cao, Y.-T.; Wu, X.-X; Cai, Y.-L.; Liu, J.; Xu, L.; Ding, K.-H.; Yu, L. Chin. Chem. Lett. 2020, 31,1078.
[8]	(a) Chen, Y.; Jing, X.; Yu, L. Chin. J. Org. Chem. 2020, 40,2570. (in Chinese)
	( 陈颖, 景崤壁, 俞磊, 有机化学,2020, 40,2570.)
	(b) Yang, Y.; Li, M.; Cao, H.; Zhang, X.; Yu, L. Mol. Catal. 2019, 474,110450.
	(c) Zhao, S.-Y.; Xu, B.-L.; Yu, L.; Fan, Y.-N. Chin. Chem. Lett. 2018, 29,884.
	(d) Zhao, S.-Y.; Xu, B.-L.; Yu, L.; Fan, Y.-N. Chin. Chem. Lett. 2018, 29,475.
	(e) Fan, X.; Yi, R.; Wang, F.; Zhang, X.; Xu, Q.; Yu, L. Chin. J. Org. Chem. 2018, 38,2736. (in Chinese)
	( 范昕, 易容, 王芳, 张旭, 徐清, 俞磊, 有机化学,2018, 38,2736.)
	(f) Zhang, D.-L.; Wei, Z.; Yu, L. Sci. Bull. 2017, 62,1325.
	(g) Tong, Q.; Gao, Q.; Xu, B.; Yu, L.; Fan, Y. Chin. J. Org. Chem. 2017, 37,753. (in Chinese)
	( 仝庆, 高强, 许波连, 俞磊, 范以宁, 有机化学,2017, 37,753.)
[9]	Rayman, M. Lancet 2012, 379,1256. doi: 10.1016/S0140-6736(11)61452-9 pmid: 22381456
[10]	Freudendahl, D.M.; Santoro, S.; Shahzad, S.A.; Santi, C.; Wirth, T. Angew. Chem., Int. Ed. 2009, 48,8409.
[11]	Cao, H.-E.; Zhu, B.-R.; Yang, Y.-F.; Xu, L.; Yu, L.; Xu, Q. Chin. J. Catal. 2018, 39 899 .
[12]	Yu, L.; Wang, J.; Chen, T.; Wang, Y.-G.; Xu, Q. Appl. Organomet. Chem. 2014, 28,652.
[13]	(a) Yu, L.; Qian, R.-R.; Deng, X.; Wang, F.; Xu, Q. Sci. Bull. 2018, 63,1010.
	(b) Zhang, H.; Han, M.-T.; Yang, C.-G.; Yu, L.; Xu, Q. Chin. Chem. Lett. 2019, 30,263.
[14]	Santoro, S.; Santi, C.; Sabatini, M.; Testaferri, L.; Tiecco, M. Adv. Synth. Catal. 2008, 350,2881.
[15]	Yu, L.; Wang, J.; Chen, T.; Ding, K.-H.; Pan, Y. Chin. J. Org. Chem. 2013, 33,1096. (in Chinese)
	( 俞磊, 王俊, 陈天, 丁克鸿, 潘毅, 有机化学,2013, 33,1096.)
[16]	Wang, Y.-G.; Yu, L.-H.; Zhu, B.-C.; Yu, L. J. Mater. Chem. A 2016, 4,10828.
[17]	Jing, X.; Yuan, D.; Yu, L. Adv. Synth. Catal. 2017, 359,1194.
[18]	(a) Yu, L.; Ye, J.-Q.; Zhang, X.; Ding, Y.-H.; Xu, Q. Catal. Sci. Technol. 2015, 5,4830.
	(b) Zhang, X.; Ye, J.; Yu, L.; Shi, X.; Zhang, M.; Xu, Q.; Lautens, M. Adv. Synth. Catal. 2015, 357,955.
[19]	(a) Deng, X.; Cao, H.-E.; Chen, C.; Zhou, H.-W.; Yu, L. Sci. Bull. 2019, 64,1280. pmid: 19777071
	(b) Deng, X.; Qian, R.; Zhou, W.; Yu, L. Chin. Chem. Lett. 2021, doi: 10.1016/j.cclet.2020.09.012. pmid: 19777071
[20]	Lee, C.-Y.; Kim, S.; Lee, K.-B.; Yoo, Y.-C.; Ryu, S.-Y.; Song, K.-S.; Arch. Pharm. Res. 2003, 26,367. pmid: 12785732
[21]	(a) Ribaudo, G.; Bellanda, M.; Menegazzo, I.; Wolters, L.P.; Bortoli, M.; Ferrer-Sueta, G.; Zagotto, G.; Orian, L. Chem.-Eur. J. 2017, 23,2405. pmid: 27935210
	(b) Goodman, M.A.; Detty, M.R. Organometallics 2004, 23,3016. pmid: 27935210
[22]	Ou, W.; Zou, R.; Han, M.-T.; Yu, L.; Su, C.-L. Chin. Chem. Lett. 2020, 31,1899.
[23]	Ribaudo, G.; Bellanda, M.; Menegazzo, I.; Wolters, L.P.; Bortoli, M.; Ferrer-Sueta, G.; Zagotto, G.; Orian, L. Chem.-Eur. J. 2017, 23,2405. pmid: 27935210
[24]	(a) Cao, H.; Qian, R.; Yu, L. Catal. Sci. Technol. 2020, 10,3113.
	(b) Liu, K.-J.; Deng, J.-H.; Yang, J.; Gong, S.-F.; Lin, Y.-W.; He, J.-Y.; Cao, Z.; He, W.-M. Green Chem. 2020, 22,433.
	(c) Xie, L.-Y.; Fang, T.-G.; Tan, J.-X.; Zhang, B.; Cao, Z.; Yang, L.-H.; He, W.-M. Green Chem. 2019, 21,3858.
[25]	(a) Nacca, F.G.; Monti, B.; Lenardão, E.J.; Evans, P.; Santi, C. Molecules 2020, 25,2018.
	(b) Peng, S.; Lin, Y.; He, W. Chin. J. Org. Chem. 2020, 40,541. (in Chinese)
	( 彭莎, 林英武, 何卫民, 有机化学,2020, 40,541.)
	(c) He, W.-B.; Gao, L.-Q.; Chen, X.-J.; Wu, Z.-L.; Huang, Y.; Cao, Z.; Xu, X.-H.; He, W.-M. Chin. Chem. Lett. 2020, 31,1895.
	(d) Xie, L.-Y.; Chen, Y.-L.; Qin, L.; Wen, Y.; Xie, J.-W.; Tan, J.-X.; Huang, Y.; Cao, Z.; He, W.-M. Org. Chem. Front. 2019, 6,3950.

聚硒醚催化环己烯氧化制备1,2-环己二醇

Polyselenide-Catalyzed Cyclohexene Oxidation to Produce 1,2-Cyclohexanediol

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 8

References 25

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Wenjian Zhou, Xinrui Xiao, Yonghong Liu, Xu Zhang. Magnetic Se/Fe/PCN-Catalyzed Oxidative Cracking Alkenes in O₂ [J]. Chinese Journal of Organic Chemistry, 2022, 42(6): 1849-1855.
[2]	Fei Yuan, Yan Zhao, Qingsong Guo, Fudan Yin, Jinrong Lai, Beifang Nian, Ming Zhang, E Tang. Synthesis of 1-[1-(Amino)cyclopropyl]ketones by Tandem Reaction Involving Vinyl Selenium Salt [J]. Chinese Journal of Organic Chemistry, 2022, 42(6): 1759-1769.
[3]	Shan Li, Yuan Cao, Lüqi Jiang. Recent Progress on Alkyl-, Aryl- and Fluoroalkyl-selenylation Reactions [J]. Chinese Journal of Organic Chemistry, 2022, 42(2): 434-457.
[4]	Tingting Yu, Dongxue Song, Ying Xu, Bing Liu, Ning Chen, Yingjie Liu. Study on the Application of Thios/Selenium Sulfonates as Radical Reagent [J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4202-4219.
[5]	Hong'en Cao, Peizi Li, Xiaobi Jing, Hongwei Zhou. Selective Epoxidation of β-Ionone Catalyzed by Iron-Doped Se/C [J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3890-3895.
[6]	Feng Liu, Jie Zhan, Yangyang Sun, Xiaobi Jing. Silver Selenide as the Novel Catalytic Material for Alcohol Oxidation [J]. Chinese Journal of Organic Chemistry, 2021, 41(5): 2099-2104.
[7]	Xin Wang, Yan Zhang, Kai Sun, Jianping Meng, Bing Zhang. Study on the Application of Photoelectric Technology in the Synthesis of Selenium-Containing Heterocycles [J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4588-4609.
[8]	Cong Wang, Yaoyao Yao, Jun Xie, Jianta Wang, Feiqing Wang, Jiquan Zhang, Lei Tang. Convenient Method for Preparingα-Ketoarylthioamide by Air Oxidation under Base Conditions [J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 370-375.
[9]	Ge Yanyu, Kong Jing, Yang Chenggen, Yang Qian, Zhang Xu. Design and Synthesis of 1,2-Bis(4-(benzyloxy)phenyl)diselane: A Scavenger for Residual Copper [J]. Chinese Journal of Organic Chemistry, 2020, 40(6): 1760-1765.
[10]	Feng Chunlai, Zhu Jie, Tang Qiujie, Zhou Aihua. Synthesis of ArSe-Substituted Flavone Derivatives Using Se Powder [J]. Chin. J. Org. Chem., 2019, 39(4): 1187-1192.
[11]	Wang Fang, Xu Lin, Sun Cheng, Xu Qing, Huang Jiejun, Yu Lei. Investigation on Preparation of p-Benzoquinone through the Organoselenium-Catalyzed Selective Oxidation of Phenol [J]. Chin. J. Org. Chem., 2017, 37(8): 2115-2118.
[12]	Zhang Xiaopeng, Jing Huanzhi, Peng Weiyu, Li Yafang, Fan Xuesen, Zhang Guisheng. Selenium-Catalyzed Carbonylation to Phenylcarbamates and Methylene Diphenyl Dicarbamates [J]. Chin. J. Org. Chem., 2017, 37(2): 411-417.
[13]	Tang Jinpeng, Tang Yu, Yang Jun, Zhang Yuanming. Selenium-Promoted Homocoupling of Grignard Reagents [J]. Chin. J. Org. Chem., 2013, 33(05): 1010-1014.
[14]	Yu Lei, Wang Jun, Chen Tian, Ding Kehong, Pan Yi. Access to Cyclohexane-1,2-diol through the Diphenyldiselenide Catalyzed Oxidation of Cyclohexene by Hydrogen Peroxide [J]. Chin. J. Org. Chem., 2013, 33(05): 1096-1099.
[15]	ZHANG Fu-Li, TANG Kun. Epoxidation of Cyclohexene Catalyzed by Metal Iron Schiff Base Complexes [J]. Chin. J. Org. Chem., 2011, 31(06): 921-924.