铑催化氢气还原RS—SR到硫酚/醇

doi:10.6023/cjoc202509036

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. 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

Thiophenols/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, the development of thiols synthesis via rhodium-catalyzed hydrogenation of RS—SR was reported. 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-catalysis, reduction, hydrogen, disulfide compound

引用此文

奚晓翔, 高明, 韩立彪. 铑催化氢气还原RS—SR到硫酚/醇[J]. 有机化学, 2026, 46(3): 859-865.

Xiaoxiang Xi, Ming Gao, Libiao Han. Rhodium-Catalyzed Reduction of RS—SR to Thiophenols/Thiols with H₂[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 859-865.

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Entry	Ligand (mol%)	Cat. (mol%)	Solvent	Yield^b/%
1	—	Rh-1 (5.0)	PhMe	84
2	—	Pt(PPh₃)₄ (5.0)	PhMe	N.R.
3	—	Pd(PPh₃)₄ (5.0)	PhMe	33
4	—	Ni(PPh₃)₄ (5.0)	PhMe	8
5	—	Rh-1 (1)	PhMe	79
6^c	—	Rh-1 (1)	PhMe	75
7^d	—	Rh-1 (1)	PhMe	70
8^e	—	Rh-1 (1)	PhMe	76
9	—	Rh-1 (0.1)	PhMe	20
10	PPh₃ (0.1)	Rh-1 (0.1)	PhMe	30
11	PPh₃ (0.3)	Rh-1 (0.1)	PhMe	30
12	—	Rh-2 (0.05)	PhMe	6
13	PPh₃ (0.15)	Rh-2 (0.05)	PhMe	8
14	dppm (0.15)	Rh-2 (0.05)	PhMe	84
15	dppe (0.15)	Rh-2 (0.05)	PhMe	99 (93^f)
16	dppf (0.15)	Rh-2 (0.05)	PhMe	23
17	dpph (0.15)	Rh-2 (0.05)	PhMe	60
18	PCy₃ (0.15)	Rh-2 (0.05)	PhMe	30
19^g	dppe (0.15)	Rh-2 (0.05)	PhMe	90
20	dppe (0.15)	Ru(OAc)₃ (0.05)	PhMe	82
21	dppe (0.15)	RuCl₃ (0.05)	PhMe	80
22	dppe (0.15)	Rh-2 (0.05)	THF	97
23	dppe (0.15)	Rh-2 (0.05)	DMF	95
24	dppe (0.15)	Rh-2 (0.05)	H₂O	70
25	dppe (0.15)	Rh-2 (0.05)	PhC₂H₅	34
26	dppe (0.15)	Rh-2 (0.05)	PhCN	88
27	dppe (0.15)	Rh-2 (0.05)	p-Xylene	97
28	dppe (0.15)	Rh-2 (0.05)	PhCl	71
29^h	dppe (0.15)	Rh-2 (0.05)	PhMe	98
30	dppe (0.15)	—	PhMe	N.R.

Entry	Ligand (mol%)	Cat. (mol%)	Solvent	Yield^b/%
1	—	Rh-1 (5.0)	PhMe	84
2	—	Pt(PPh₃)₄ (5.0)	PhMe	N.R.
3	—	Pd(PPh₃)₄ (5.0)	PhMe	33
4	—	Ni(PPh₃)₄ (5.0)	PhMe	8
5	—	Rh-1 (1)	PhMe	79
6^c	—	Rh-1 (1)	PhMe	75
7^d	—	Rh-1 (1)	PhMe	70
8^e	—	Rh-1 (1)	PhMe	76
9	—	Rh-1 (0.1)	PhMe	20
10	PPh₃ (0.1)	Rh-1 (0.1)	PhMe	30
11	PPh₃ (0.3)	Rh-1 (0.1)	PhMe	30
12	—	Rh-2 (0.05)	PhMe	6
13	PPh₃ (0.15)	Rh-2 (0.05)	PhMe	8
14	dppm (0.15)	Rh-2 (0.05)	PhMe	84
15	dppe (0.15)	Rh-2 (0.05)	PhMe	99 (93^f)
16	dppf (0.15)	Rh-2 (0.05)	PhMe	23
17	dpph (0.15)	Rh-2 (0.05)	PhMe	60
18	PCy₃ (0.15)	Rh-2 (0.05)	PhMe	30
19^g	dppe (0.15)	Rh-2 (0.05)	PhMe	90
20	dppe (0.15)	Ru(OAc)₃ (0.05)	PhMe	82
21	dppe (0.15)	RuCl₃ (0.05)	PhMe	80
22	dppe (0.15)	Rh-2 (0.05)	THF	97
23	dppe (0.15)	Rh-2 (0.05)	DMF	95
24	dppe (0.15)	Rh-2 (0.05)	H₂O	70
25	dppe (0.15)	Rh-2 (0.05)	PhC₂H₅	34
26	dppe (0.15)	Rh-2 (0.05)	PhCN	88
27	dppe (0.15)	Rh-2 (0.05)	p-Xylene	97
28	dppe (0.15)	Rh-2 (0.05)	PhCl	71
29^h	dppe (0.15)	Rh-2 (0.05)	PhMe	98
30	dppe (0.15)	—	PhMe	N.R.