Photochemical Reduction of Nitroaromatics Mediated by p-Toluenethiol/PCy3

doi:10.6023/cjoc202109037

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (12): 4773-4779.DOI: 10.6023/cjoc202109037 Previous Articles Next Articles

Special Issue: 有机光催化虚拟合辑；绿色合成化学专辑；热点论文虚拟合集

ARTICLES

对甲苯硫酚/三环己基膦介导的硝基芳烃的光化学还原反应

鲍兆伟, 吕洁, 金智超^*()

贵州大学绿色农药与农业生物工程国家重点实验室培育基地教育部绿色农药与农业生物工程重点实验室贵阳 550025

收稿日期:2021-09-24 修回日期:2021-10-26 发布日期:2021-11-03
通讯作者: 金智超
基金资助:
国家自然科学基金(21801051); 国家自然科学基金(21961006); 国家自然科学基金(32172459); 贵州省科技技术基金(黔科合基础-ZK[2021]重点033)

Photochemical Reduction of Nitroaromatics Mediated by p-Toluenethiol/PCy₃

Zhaowei Bao, Jie Lü, Zhichao Jin()

State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Guiyang 550025

Received:2021-09-24 Revised:2021-10-26 Published:2021-11-03
Contact: Zhichao Jin
Supported by:
National Natural Science Foundation of China(21801051); National Natural Science Foundation of China(21961006); National Natural Science Foundation of China(32172459); Science and Technology Department of Guizhou Province(黔科合基础-ZK[2021]重点033)

1. .pdf(5630KB)

Abstract

A new photochemical reduction of nitroaromatics mediated by p-toluenethiol and PCy₃ under solvent-free, metal-free, and mild conditions is reported for the first time. This reaction has shown good generalities, and amine derivatives with different substituents and substitution patterns can be obtained in good yields. Therefore, this reduction method represents a potentially valuable new strategy for the efficient synthesis of amine compounds.

Key words: nitroaromatics, reduction, photochemistry, aromatic amines

Cite this article

Zhaowei Bao, Jie Lü, Zhichao Jin. Photochemical Reduction of Nitroaromatics Mediated by p-Toluenethiol/PCy₃[J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4773-4779.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 5

Scheme 1. Reduction of nitroaromatic compounds

Entry	P	Solvent	Additive	Yield^b/%
1	P₁	H₂O	A	67
2	P₂	H₂O	A	50
3	P₃	H₂O	A	75
4	P₄	H₂O	A	66
5	P₃	MeOH	A	55
6	P₃	i-PrOH	A	13
7	P₃	H₂O	B	69
8	P₃	H₂O	C	0
9	P₃	H₂O	D	0
10 ^c	P₃	H₂O	A	93
11 ^c	P₃	—	A	98

Table 1. Condition optimization for the reduction of the nitroarene 1a

Table 2. Evaluation of substrate scope for the reduction of nitro the compounds

Scheme 2. Synthesis at 1.0 mmol scale and reaction using sunlight as light source

Scheme 3. Proposed reaction mechanism for the reduction of the nitro arene

References 22

[1]	(a) Zhu, S.; Xu, S.; Jing, W.; Zhao, Z.; Jiang, J. J. Agric. Food Chem. 2016, 64, 9702. doi: 10.1021/acs.jafc.6b03977
	(b) Liu, X. H.; Wen, Y. H.; Cheng, L.; Xu, T. M.; Wu, N. J. J. Agric. Food Chem. 2021, 69, 6968. doi: 10.1021/acs.jafc.1c00236
[2]	(a) Ye, L. J.; Toh, H. H.; Yang, Y.; Adams, J. P.; Snajdrova, R.; Li, Z. ACS Catal. 2015, 5, 1119. doi: 10.1021/cs501906r
	(b) Werner, L.; Machara, A.; Hudlicky, T. Adv. Synth. Catal. 2010, 352, 195. doi: 10.1002/adsc.v352:1
	(c) Das Sarma, K.; Zhang, J.; Huang, Y.; Davidson, J. G. Eur. J. Org. Chem. 2006, 2006, 3730. doi: 10.1002/(ISSN)1099-0690
[3]	(a) Lin, C.-F.; Chien, C.-W.; Ojima, I. Org. Chem. Front. 2014, 1, 1062. doi: 10.1039/C4QO00180J pmid: 31633341
	(b) Afanasyev, O. I.; Kuchuk, E.; Usanov, D. L.; Chusov, D. Chem. Rev. 2019, 119, 11857. doi: 10.1021/acs.chemrev.9b00383 pmid: 31633341
[4]	(a) Strotman, N. A.; Baxter, C. A.; Brands, K. M.; Cleator, E.; Krska, S. W.; Reamer, R. A.; Wallace, D. J.; Wright, T. J. J. Am. Chem. Soc. 2011, 133, 8362. doi: 10.1021/ja202358f pmid: 21528938
	(b) Magnus, P.; Sane, N.; Fauber, B. P.; Lynch, V. J. Am. Chem. Soc. 2009, 131, 16045. doi: 10.1021/ja9085534 pmid: 21528938
	(c) Cox, C. D.; Breslin, M. J.; Whitman, D. B.; Schreier, J. D.; McGaughey, G. B.; Bogusky, M. J.; Roecker, A. J.; Mercer, S. P.; Bednar, R. A.; Lemaire, W.; Bruno, J. G.; Reiss, D. R.; Harrell, C. M.; Murphy, K. L.; Garson, S. L.; Doran, S. M.; Prueksaritanont, T.; Anderson, W. B.; Tang, C.; Roller, S.; Cabalu, T. D.; Cui, D.; Hartman, G. D.; Young, S. D.; Koblan, K. S.; Winrow, C. J.; Renger, J. J.; Coleman, P. J. J. Med. Chem. 2010, 53, 5320. doi: 10.1021/jm100541c pmid: 21528938
	(d) Baxter, C. A.; Cleator, E.; Brands, K. M. J.; Edwards, J. S.; Reamer, R. A.; Sheen, F. J.; Stewart, G. W.; Strotman, N. A.; Wallace, D. J. Org. Process Res. Dev. 2011, 15, 367. doi: 10.1021/op1002853 pmid: 21528938
[5]	(a) Xu, D.-Q.; Hu, Z.-Y.; Li, W.-W.; Luo, S.-P.; Xu, Z.-Y. J. Mol. Catal. A: Chem. 2005, 235, 137. doi: 10.1016/j.molcata.2005.04.004 pmid: 27515391
	(b) Wu, G.; Huang, M.; Richards, M.; Poirier, M.; Wen, X.; Draper, R. W. Synthesis 2003, 1657. pmid: 27515391
	(c) Xu, S.; Tang, J.; Zhou, Q.; Du, J.; Li, H. ACS Sustainable Chem. Eng. 2019, 7, 16190. doi: 10.1021/acssuschemeng.9b03149 pmid: 27515391
	(d) Xiao, Q.; Sarina, S.; Waclawik, E. R.; Jia, J.; Chang, J.; Riches, J. D.; Wu, H.; Zheng, Z.; Zhu, H. ACS Catal. 2016, 6, 1744. doi: 10.1021/acscatal.5b02643 pmid: 27515391
	(e) Tsutsumi, K.; Uchikawa, F.; Sakai, K.; Tabata, K. ACS Catal. 2016, 6, 4394. doi: 10.1021/acscatal.6b00886 pmid: 27515391
	(f) Park, Y.; Kim, Y.; Chang, S. Chem. Rev. 2017, 117, 9247. doi: 10.1021/acs.chemrev.6b00644 pmid: 27515391
	(g) Pachisia, S.; Kishan, R.; Yadav, S.; Gupta, R. Inorg. Chem. 2021, 60, 2009. doi: 10.1021/acs.inorgchem.0c03505 pmid: 27515391
	(h) Liu, Y.; Miao, W.; Tang, W.; Xue, D.; Xiao, J.; Wang, C.; Li, C. Chem. Asian J. 2021, 16, 1725. doi: 10.1002/asia.v16.13 pmid: 27515391
	(i) Gutiérrez-Tarriño, S.; Rojas-Buzo, S.; Lopes, C. W.; Agostini, G.; Calvino, J. J.; Corma, A.; Oña-Burgos, P. Green Chem. 2021, 23, 4490. doi: 10.1039/D1GC00706H pmid: 27515391
	(j) Cheung, C. W.; Hu, X. Nat. Commun. 2016, 7, 12494. doi: 10.1038/ncomms12494 pmid: 27515391
	(k) Blaser, H.-U.; Steiner, H.; Studer, M. ChemCatChem 2009, 1, 210. doi: 10.1002/cctc.v1:2 pmid: 27515391
[6]	(a) Gao, Y.; Ma, D.; Wang, C.; Guan, J.; Bao, X. Chem. Commun. 2011, 47, 2432. doi: 10.1039/C0CC04420B pmid: 26262554
	(b) Giomi, D.; Alfini, R.; Brandi, A. Tetrahedron 2011, 67, 167. doi: 10.1016/j.tet.2010.11.008 pmid: 26262554
	(c) Li, B.; Xu, Z. J. Am. Chem. Soc. 2009, 131, 16380. doi: 10.1021/ja9061097 pmid: 26262554
	(d) Orlandi, M.; Benaglia, M.; Tosi, F.; Annunziata, R.; Cozzi, F. J. Org. Chem. 2016, 81, 3037. doi: 10.1021/acs.joc.6b00191 pmid: 26262554
	(e) Orlandi, M.; Tosi, F.; Bonsignore, M.; Benaglia, M. Org. Lett. 2015, 17, 3941. doi: 10.1021/acs.orglett.5b01698 pmid: 26262554
	(f) Sharma, S.; Kumar, M.; Kumar, V.; Kumar, N. J. Org. Chem. 2014, 79, 9433. doi: 10.1021/jo5019415 pmid: 26262554
[7]	Pirola, M.; Faverio, C.; Orlandi, M.; Benaglia, M. Chem.-Eur. J. 2021, 27, 10247. doi: 10.1002/chem.v27.40
[8]	Porwal, D.; Oestreich, M. Eur. J. Org. Chem. 2016, 2016, 3307. doi: 10.1002/ejoc.v2016.20
[9]	Freeman, A. W.; Urvoy, M.; Criswell, M. E. J. Org. Chem. 2005, 70, 5014. pmid: 15960500
[10]	Duan, Z.; Ranjit, S.; Liu, X. Org. Lett. 2010, 12, 2430. doi: 10.1021/ol100816g
[11]	Shi, J.; Wei, W. Chin. J. Org. Chem. 2020, 40, 2170. (in Chinese) doi: 10.6023/cjoc202000041
	( 时建伟, 魏伟, 有机化学, 2020, 40, 2170.) doi: 10.6023/cjoc202000041
[12]	(a) Peng, S.; Lin, Y.; He, W.-M. Chin. J. Org. Chem. 2020, 40, 541. (in Chinese) doi: 10.6023/cjoc202000006
	( 彭莎, 林英武, 何卫民, 有机化学, 2020, 40, 541.) doi: 10.6023/cjoc202000006
	(b) Chen, D.; Sun, Y.; Dong, D.; Han, Q.; Wang, Z. Chin. J. Org. Chem. 2020, 40, 4267. (in Chinese) doi: 10.6023/cjoc202006025
	( 陈德茂, 孙媛媛, 董道青, 韩晴晴, 王祖利, 有机化学, 2020, 40, 4267.) doi: 10.6023/cjoc202006025
	(c) Ge, L.; Chiou, M.-F.; Li, Y.; Bao, H. Green Synth. Catal. 2020, 1, 86.
	(d) Cao, D.; Pan, P.; Li, C.-J.; Zeng, H. Green Synth. Catal. 2021, 2, 303.
	(e) Wang, P.; Zhao, Q.; Xiao, W.; Chen, J. Green Synth. Catal. 2020, 1, 42.
	(f) Tong, S.; Li, K.; Ouyang, X.; Song, R.; Li, J. Green Synth. Catal. 2021, 2, 145.
[13]	(a) Wang, Z.; Liu, Q.; Liu, R.; Ji, Z.; Li, Y.; Zhao, X.; Wei, W. Chin. Chem. Lett. 2021 DOI: 10.1016/j.cclet.2021.08.036. doi: 10.1016/j.cclet.2021.08.036
	(b) Meng, N.; Lv, Y.; Liu, Q.; Liu, R.; Zhao, X.; Wei, W. Chin. Chem. Lett. 2021, 32, 258. doi: 10.1016/j.cclet.2020.11.034
	(c) Wang, L.; Bao, P.; Liu, W.; Liu, S.; Hu, C.; Yue, H.; Yang, D.; Wei, W. Chin. J. Org. Chem. 2018, 38, 3189. (in Chinese) doi: 10.6023/cjoc201807014
	( 王雷雷, 鲍鹏丽, 刘维伟, 刘思彤, 胡昌松, 岳会兰, 杨道山, 魏伟, 有机化学, 2018, 38, 3189.) doi: 10.6023/cjoc201807014
	(d) Bao, P.; Liu, F.; Lv, Y.; Yue, H.; Li, J.-S.; Wei, W. Org. Chem. Front. 2020, 7, 492. doi: 10.1039/C9QO01334B
[14]	(a) Jin, W.; Liu, C. Chin. J. Org. Chem. 2021, 41, 2148. (in Chinese)
	( 金伟伟, 刘晨江, 有机化学, 2021, 41, 2148.) doi: 10.6023/cjoc202100038
	(b) Gui, Q.-W.; Teng, F.; Li, Z.-C.; Xiong, Z.-Y.; Jin, X.-F.; Lin, Y.-W.; Cao, Z.; He, W.-M. Chin. Chem. Lett. 2021, 32, 1907. doi: 10.1016/j.cclet.2021.01.021
	(c) Sun, K.; Xiao, F.; Yu, B.; He, W.-M. Chin. J. Catal. 2021, 42, 1921. doi: 10.1016/S1872-2067(21)63850-0
[15]	Qu, Z.; Chen, X.; Zhong, S.; Deng, G. J.; Huang, H. Org. Lett. 2021, 23, 5349. doi: 10.1021/acs.orglett.1c01654
[16]	Smolinsky, G.; Feuer, B. I. J. Org. Chem. 1966, 31, 3882. doi: 10.1021/jo01349a530
[17]	Zhao, L.; Hu, C.; Cong, X.; Deng, G.; Liu, L. L.; Luo, M.; Zeng, X. J. Am. Chem. Soc. 2021, 143, 1618. doi: 10.1021/jacs.0c12318
[18]	Li, J.; Shi, X.-Y.; Bi, Y.-Y.; Wei, J.-F.; Chen, Z.-G. ACS Catal. 2011, 1, 657. doi: 10.1021/cs200105u
[19]	Wienhofer, G.; Sorribes, I.; Boddien, A.; Westerhaus, F.; Junge, K.; Junge, H.; Llusar, R.; Beller, M. J. Am. Chem. Soc. 2011, 133, 12875. doi: 10.1021/ja2061038
[20]	Yao, W.; Wang, J.; Lou, Y.; Wu, H.; Qi, X.; Yang, J.; Zhong, A. Org. Chem. Front. 2021, 8, 4554. doi: 10.1039/D1QO00705J
[21]	Formenti, D.; Ferretti, F.; Topf, C.; Surkus, A.-E.; Pohl, M.-M.; Radnik, J.; Schneider, M.; Junge, K.; Beller, M.; Ragaini, F. J. Catal. 2017, 351, 79. doi: 10.1016/j.jcat.2017.04.014
[22]	Lu, H.; Geng, Z.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Org. Lett. 2016, 18, 2774. doi: 10.1021/acs.orglett.6b01274

对甲苯硫酚/三环己基膦介导的硝基芳烃的光化学还原反应

Photochemical Reduction of Nitroaromatics Mediated by p-Toluenethiol/PCy₃

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 5

References 22

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Boyu Yan, Jieliang Wu, Jinfei Deng, Dan Chen, Xiushen Ye, Qiuli Yao. Recent Progress in Light-Driven Direct Dehydroxylation and Derivation of Alcohols [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3055-3066.
[2]	Xiangping Chen, Chenxiang Meng, Mengna Li, Shangmin Chu, Xinxin Zhu, Kai Xu, Lantao Liu, Tao Wang, Fenghua Zhang, Fei Li. Fe-Catalyzed Synthesis of Sulfide-Based Aromatic Primary Amines in Water Promoted by Sodium-Ascorbate [J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2800-2807.
[3]	Linlin Du, Hua Zhang. Photochemical and Electrochemical Borylation Involving Aryl and Alkyl Compounds [J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1726-1741.
[4]	Miaomiao Zhang, Rong Chen, Hongmei Jiao, Haojie Ma, Bo Han, Yuqi Zhang, Jijiang Wang. MgCl₂-Catalyzed Chemoselective Reduction of Aldehydes, Ketones and Imines [J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1462-1471.
[5]	Guanghui Shi, Yunzhe Du, Yuanyuan Gao, Huijie Jia, Hailong Hong, Limin Han, Ning Zhu. Reduction of Nitro Group by Sulfide and Its Applications in Amine Synthesis [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 491-502.
[6]	Yushan Zhang, Zhen Huan, Jindong Yang, Jinpei Cheng. Recent Advances in Hydrogen Transfer Reactivities of N-Heterocyclic Phosphines [J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3806-3825.
[7]	Xiangkun Meng, Zhengyuan Qi, Lei Yu, Yiyang Zhang. Catalytic System for Poly(lactic acid) Synthesis: Opportunities and Challenges [J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 112-119.
[8]	Wensheng Zhang, Yan Li, Haiyan Cui, Xiaoli Su, Supeng Xu. One-Pot Synthesis of N-Substituted Isoindolin-1-ones via Reductive Amination/Lactamization of Methyl 2-Formylbenzoate [J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2456-2461.
[9]	Yiwen Guan, Kejian Chang, Qianlin Sun, Xin Xu. Progress in Rare-Earth Metal-Based Lewis Pair Chemistry [J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1326-1335.
[10]	Jintao Wu, Zhongquan Liu. Advances in Free-Radical Promoted C(sp³)—C(sp³) Bond Conversion [J]. Chinese Journal of Organic Chemistry, 2022, 42(1): 16-32.
[11]	Xingyue Wang, Changlin Xu, Hongyu Guan, Mi Lin, Peng Huang. Deoxygenation of Sulfoxides with Dimethylthiocarbamoyl Chloride in the Absence of Additional Solvent [J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3330-3334.
[12]	Linlin Li, Xiaoyu Chen, Congcong Pei, Jingya Li, Dapeng Zou, Yangjie Wu, Yusheng Wu. Transition Metal-Free Deuteride Reduction of N-tert-Butanesulfinyl Ketimines Derivatives via B₂pin₂/D₂O System [J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2319-2325.
[13]	Chen Liu, Yan Qi, Yongjun Liu. Recent Development of Samarium Diiodide and Other Samarium Reagents in Organic Transformation [J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2202-2216.
[14]	Hao Wang, Ping Ying, Jingbo Yu, Weike Su. Alternative Strategies Enabling Cross-Dehydrogenative Coupling: Access to C—C Bonds [J]. Chinese Journal of Organic Chemistry, 2021, 41(5): 1897-1924.
[15]	Yuhang He, Hui Yang, Dongxu Gao, Jiahui Ma, Yamin Shao, Guanghui An, Guangming Li. Visible Light-Mediated Metal-Free Decarboxylative Deuteration of Carboxylic Acid [J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4725-4731.