Rhodium-catalyzed reduction of RS-SR to RSH with H2

doi:10.6023/cjoc202509036

Chinese Journal of Organic Chemistry Previous Articles Next Articles

ARTICLE

铑催化氢气还原RS-SR到硫/醇

奚晓翔^a,b, 高明^b, 韩立彪^*,a,b

^a绍兴文理学院化学化工学院浙江省精细化学品传统工艺替代技术研究实验室浙江绍兴 312000
^b浙江扬帆新材料股份有限公司浙江上虞 312369

收稿日期:2025-09-28 修回日期:2025-12-16
基金资助:
浙江省领军型创新创业团队基金(2022R01021)项目

Rhodium-catalyzed reduction of RS-SR to RSH with H₂

Xiaoxiang Xi^a,b, Ming Gao^b, Libiao Han^*,a,b

^aZhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process, School of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing 312000, China
^bZhejiang Yangfan New Materials Co., Ltd., Shangyu, Zhejiang 312369

Received:2025-09-28 Revised:2025-12-16
Contact: *E-mail: hlb@shoufuchem.com
Supported by:
Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang (2022R01021)

1. .pdf(1688KB)

Abstract

Thiols are important building blocks for the synthesis of a variety of pharmaceutically important sulfur-containing compounds. Due to the versatile functionalities in organic synthesis, Herein, we report the development of thiols synthesis via rhodium-catalyzed hydrogenation of RS-SR. Green and clean hydrogen is used as the reductant. This transformation exhibits excellent functional group tolerance, a wide range of aryl or alkyl disulfides were reduced to the corresponding thiols in good to excellent yields with a loading of rhodium catalysts down to 0.05 mol%. This reaction also can be carried out at a large gram scale. And the catalysts can be recycled three times without diminishing the catalytic activity. All of these show that this method for hydrogenation of disulfide has great potential for industrial production.

Key words: Rhodium-catalyzed, Reduction, Hydrogen, Disulfide compounds

Cite this article

Xiaoxiang Xi, Ming Gao, Libiao Han. Rhodium-catalyzed reduction of RS-SR to RSH with H₂[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202509036.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Koval, I. V. Russ. J. Org. Chem.2005, 41, 631-648.(b) Uchiro H.; Kobayashi S. Tetrahedron Lett.1999, 40, 3179-3182.(c) Testaferri, L.; Tingoli, M.; Tiecco, M. Tetrahedron Lett. 1980, 21, 3099-3100. (d) Oae, S.; Togo, H. Tetrahedron Lett. 1982, 23, 4701-4704. (e) Hong, S.-M.; Kim, O.; Hwang, S.-H. Materials 2024, 17, 1343.
[2] Our recently work on the synthesis of organophosphorus: (a) Zhang, J. Q; Wang, X.; Wang T.; Chen T.; Han, L. B. Green Chem,2023, 25, 9063-9068.(b) Ma X.; Yan, X. Jing, Y.; Guo, J.; Bian, J.; Yan, R.; Xu, Q.; Han L. B. Green Chem., 2025, 27, 102-108.(c) Zhang, J. Hu, W.; Chen, Z.; Wu, N.; Li, C.; Chen, T.; Han L. B. Org. Lett. 2024, 26, 3386-3390. (d) Wang, J.; Xiao, J.; Tang, Z. L.; Lan, D. H.; Han, L. B. J. Org. Chem. 2024, 89, 5109-5117. (e) Zhang, J. Q.; Han L. B. J. Org. Chem. 2024, 89, 2090-2103.
[3] Liang J.; Yang Y.; Liu J.; Xu, Q. Han. L. B. Chin. J. Org. Chem.,2024, 44, 1658-1666.
[4] (a) Boström, J.; Brown, D.; Young, R.; Keserü, G. M.Nat. Rev. Drug Discov. 2018. 717, 09-727.(b) Li G.; Lou, H.-X. Med. Res. Rev.2018, 38, 1255-1294. (c) Trivedi, M. V.; Laurence, J. S.; Siahaan, T.Curr. Protein Pept. Sci. 2009, 10, 614-625.(d) Vericat, C.; Vela, M. E.; Benitez, G.; Carro, P.; Salvarezza, R. C. Chem. Soc. Rev. 2010, 39, 1805-1834. (e) Feng, M.; Tang, B.; Liang, S. H.; Jiang, X. Curr. Top. Med. Chem. 2016, 16, 1200-1216.
[5] Examples of thiophenol conversion to thioether: (a) Eduardo J.-R.; Hugo V.; Simon H.-O.; Rosa M.; Marcel S.; David M.-M. J. Catal.2023, 426, 247-256.(b) Jati A.; Dam S.; Kumar S.; Kumar K.; Maji B. Chem. Sci.2023, 14, 8624-8634.(c) Ji, H.; Cao, H.; Wang, G.; Xing, F.; Szostak, M.; Liu, C. Org. Chem. Front. 2023, 10, 4275-4281. (d) Oechsner, R. M.; Lindenmaier, I. H.; Fleischer, I. Org. Lett. 2023, 25, 1655-1660. (e) Xu, T.; Zhou, X.; Xiao, X.; Yuan, Y.; Liu, L.; Huang, T.; Li, C.; Tang, Z.; Chen, T Q. J. Org. Chem., 2022, 87, 8672-8648.
[6] Examples of thiophenol conversion to sulfoxides: (a) Liu Q.; Wang L.; Yue H.; Li J.-S.; Luo Z.; Wei W. Green Chem.,2019, 21, 1609-1613.(b) Hou Y.-J.; Li Y.; Zhao Z.-W.; Fan T.-G.; Sun B.-X.; Wang X.-N.; Li, Y.-M. Org. Lett. 2023 25, 517-521. (c) Kim D. H.; Lee J.; Lee A. Org. Lett.2018, 20, 764-767.
[7] Shyam P. K.; Kim Y. K.; Lee C.; Jang, H.-Y. Adv. Synth. Catal.2016, 358, 56-61.
[8] Examples of thiophenol conversion to sulfoxides: (a) Laudadio G.; Bartolomeu A. de A.; Verwijlen L. M. H. M.; Cao Y.; de Oliveira K. T.; Noel, T. J. Am. Chem. Soc.2019, 141, 11832-11836.(b) Wang L.; Cornella, J. Angew. Chem. Int. Ed.2020, 59, 23510-23515 (c) Yamahara, S.; Salem, M. S. H.; Kawai, T.; Watanabe, M.; Sakamoto, Y.; Okada, T.; Kimura, Y.; Takizawa, S.; Kirihara, M. ACS Sustainable Chem. Eng. 2024, 12, 12135-12142.
[9] Deryagina E. N.; Sukhomasova E. N.; Levanova E. P.; Papernaya L. K.; Korchevin N. A.Russ. J. Org. Chem. 2005, 41, 1624-1630.
[10] (a) Dougherty, G.; Hammond, P. D.J. Am. Chem. Soc. 1935, 57, 117-118.
[11] A patent of our company about the reactin of benzene and elemental sulfur: Fan, B.; Zhang, Z.; Liao, Z.; Lv, X.; Tao, M.; Yuan, J. patent China CN 108863867A, 2018.
[12] Example of Matal promote reductive cleavage of the S-S: (a) Zhang, M.; Ryckman, D.; Chen, G. E. MacMillan, J. Duquette.Synthesis 2003, 0112-0116.(b) Erlandsson, M., Hällbrink, M. Int J Pept Res Ther.2005, 11, 261-265.(c) Sridhar, M.; Vadivel, S. K.; Bhalerao, U. T. Synth. Commun., 1997, 27, 1347-1350.
[13] Selected example of reductive cleavage of the S-S with hydrides: (a) Brown H. C.; Nazer B.; Cha Jin S. Synthesis1984, 6, 498-500.(b) Yoon N. M.; Gyoung, Y. S. J. Org. Chem.1985, 50, 2443-2450.(c) Ookawa, A.; Yokoyama, S.; Soai, K. Synth. Commun., 1986, 16, 819-825.(d) Kolmakov, K. A.; Kresge, A. J. Can. J. Chem. 2008, 86, 119-123. (e) Kong, F.; Zhou, X. Synth. Commun. 1989, 19, 3143-3149.
[14] Maiti S. N.; Spevak P.; Singh M.; Micetich R. G.; Reddy, A. V. N. Synth. Commun.1988, 18, 575-581.
[15] (a) Overman L. E.; Matzinger D.; O’Connor E. M.; Overman, J. D. J. Am. Chem. Soc.1974, 96, 6081-6089.(b) Overman L.E.; Petty, S. T. J. Org. Chem.1975, 40, 2779-2782.
[16] Bai L.; Jiang X.CCS Chem. 2025, 7, 1889-1902.
[17] (a) Calais C., Lacroix M., Geantet C., Breysse M. J. Catal.1993, 144, 160-174.(b) McLaughlin, L.; Novakova, E.; Burchand, R.; Hardacre, C.Appl. Catal. A Gen. 2008, 340, 162-168.(c) Novakova, E.; McLaughlin, L.; Burch, R.; Crawford, P.; Griffin, K.; Hardacre, C.; Hu, P.; Rooney; D. J. Catal., 2007, 249, 93-101.
[18] Arisawa M.; Sugata C.; Yamaguchi M. Tetrahedron Lett.2005, 46, 6097-6099.
[19] (a) Arisawa M.; Yamaguchi M. Molecules2020, 25, 3595.(b) Arisawa, M.; Suwa, A.; Fujimoto, K.; Yamaguchi, M.Adv. Synth. Catal. 2003, 345, 560-563.
[20] Malviya B. K.; Hansen E. C.; Kong C. J.; Imbrogno J.; J. Verghese; Guinness, S. M.; Salazar C. A.; Desrosiers J. N.; Kappe C. O.; Cantillo, D. Chem. Eur. J.2023, 29, e202302664.
[21] Chen X.; Zhou S.; Qian, C. J. Sulfur Chem.2012, 33, 179-185.
[22] Martin D. P.; Cohen, S. M. Chem. Commun.,2012, 48, 5259-5261.
[23] Liu Y.; Kim J.; Seo H.; Park S.; Chae, J. Adv. Synth. Catal.2015, 357, 2205-2212.
[24] Chaudhary S.; Marilyn D. M.; Garg P. A ChemistrySelect.2017, 2, 650-654.

铑催化氢气还原RS-SR到硫/醇

Rhodium-catalyzed reduction of RS-SR to RSH with H₂

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Tianqing Zhang, Xiuming Wu, Congcong Wang. Research Progress of Low-Coordinate Phosphenium Ions Compounds [J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3244-3254.
[2]	Wen Xu, Meiming Luo, Xiaoming Zeng. Cr-Catalyzed Reductive Cross-Coupling of Trifluoromethyl Alkenes [J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3401-3411.
[3]	Youxue Zhao, Xiruo Li, Luobing Meng, Chunxiu Li, Guisheng Fan, Jianhe Xu. Advances in Understanding the Substrate Promiscuity of Alcohol Dehydrogenases/Carbonyl Reductases^★ [J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3175-3185.
[4]	Yinsheng Miao, Lei Zhang, Jianqi Chen, Lili Wang, Zheng Duan. Synthesis of Pyrazolo(iso)quinoline Derivatives from Aryl Alkynes and N-Imine(iso)quinoline Ylides Catalyzed by Bisphosphonium Salt [J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2876-2884.
[5]	Shunli Du, Yaya Wang, Jiaming Guo, Xuewei Xu, Xinhua Peng. Study on the Borylation of β-C Positions of Aryl Olefins Catalyzed by Copper Organophosphorus Complexes [J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2435-2443.
[6]	Chunyang Hu, Yasir Mumtaz, Khan Jahangir, Leibing Wang, Lvqi Jiang. HCF₂SO₂Na: a New Application as a Thioformylation Reagent for Amines [J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 2171-2180.
[7]	Yan Yao, Niankai Fu. Recent Advances in Electrophotochemical Transition Metal Catalysis [J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 1819-1837.
[8]	Jiangyan Tian, Chi Li, Jianfei Chen, Hui Lv. Nickel and Cobalt-Catalyzed Asymmetric Reductive Coupling of Halides with Aldehydes, Ketones and Imines [J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 1946-1960.
[9]	Shentong Xie, Wenjing Li, Yu Liu, Xi Lu, Renyi Shi. Ni-Catalyzed Reductive Alkylation of Polyfluoroarenes with Alkyl Halides [J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 2121-2127.
[10]	Hui Li, Ablimit Abdukader, Lei Zhou. Radical Denitrogenative Ring Opening of N-Benzyl-benzotriazoles for the Synthesis of 6-Substituted Phenanthridines under Visible Light Conditions [J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1770-1777.
[11]	Ang Gao, Luyu Yan, Guangzu Wang, Mingchen Fu. Photoinduced Decarboxylative Amination Driven by Electron Donor-Acceptor Complex [J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1747-1754.
[12]	Yang Hong, Hongping Deng. Research Progress on Photocatalyzed Protic C(sp³)—HFunctionalization [J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1569-1590.
[13]	Chen Li, Yi Jiao, Xiaoran Shi, Yiqiang Yang, Shouyun Yu. Photoredox-Catalyzed C-Glycosylation Reactions [J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1423-1459.
[14]	Junjie Liu, Hongping Zhao, Yuanyuan Hu, Hengxin Wang, Weiming Yuan. Photoinduced Nickel-Catalyzed Reductive Heck Reaction [J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1691-1697.
[15]	Jieqing Ou, Peizhen Qu, Liang Zhao. Visible Light Mediated Palladium-Catalyzed Hydrodebromination of Aliphatic α-Bromotrifluoromethyl Compounds [J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1334-1341.