铑催化氢气还原RS-SR到硫/醇

doi:10.6023/cjoc202509036

研究论文

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)

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摘要/Abstract

有机硫酚/醇是构建含硫化合物的合成砌块,在有机合成化学中占有重要的地位。本文报道了铑催化氢气还原二硫醚类化合物制备硫酚/醇的新方法。该反应底物适用范围广并展现出良好的官能团耐受性,多种芳基或烷基二硫醚类化物均能以良好至优异的产率被还原为相应硫酚/醇。此外,该方法还可以放大至克级反应规模,铑催化剂负载量可低至0.05 mol%。最后,所报道的铑催化体系可循环套用三次,其催化活性不衰减。上述研究表明这种铑催化还原二硫醚类化合物的方法具有潜在的工业应用价值。

关键词: 铑催化, 还原, 氢气, 二硫醚类化合物

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

引用此文

奚晓翔, 高明, 韩立彪. 铑催化氢气还原RS-SR到硫/醇[J]. 有机化学, doi: 10.6023/cjoc202509036.

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.

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参考文献

[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.