Efficient Hydrogenation of Ketones to Alcohols Catalysed by Phosphinoamine Rhenium Complexes

doi:10.6023/cjoc202506024

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (1): 241-249.DOI: 10.6023/cjoc202506024 Previous Articles Next Articles

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膦胺铼配合物催化酮加氢制醇性能研究

方霄龙^a^,^*(), 王俊^a, 徐舒婷^a, 李浩^a, 胡坤^a, 陈宜瑜, Yiyu^b

^a 安徽建筑大学功能分子设计与界面过程重点实验室合肥 230601
^b 安徽建筑大学建筑与规划学院合肥 230601

收稿日期:2025-06-18 修回日期:2025-07-22 发布日期:2025-09-03
通讯作者: 方霄龙
基金资助:
国家自然科学基金(21802010); 国家自然科学基金(22401003); 安徽省自然科学基金(2308085MB49); 及安徽省教育厅优秀青年基金(2023AH030038)

Efficient Hydrogenation of Ketones to Alcohols Catalysed by Phosphinoamine Rhenium Complexes

Fang Xiaolong^a^,^*(), Wang Jun^a, Xu Shuting^a, Li Hao^a, Hu Kun^a, Chen, Yiyu^b

^a Key Laboratory of Functional Molecule Design and Interface Process, Anhui Jianzhu University, Hefei 230601
^b School of Architecture and Urban Planning, Anhui Jianzhu University, Hefei 230601

Received:2025-06-18 Revised:2025-07-22 Published:2025-09-03
Contact: Fang Xiaolong
Supported by:
Natural Science Foundation of China(21802010); Natural Science Foundation of China(22401003); Natural Science Foundation of Anhui Province(2308085MB49); Fund for Outstanding Young Scholars of Anhui Province(2023AH030038)

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Abstract

Rhenium complexes (Ph₂PCH₂CH₂NH₂)Re(CO)₃Cl (1), (Ph₂PCH₂CH₂CH₂NH₂)Re(CO)₃Cl (2), (o-Ph₂PC₆H₄NH₂)- Re(CO)₃Cl (3), [(Ph₂PCH₂CH₂NH₂)₂Re(CO)₂]Cl (4), [(Ph₂PCH₂CH₂CH₂NH₂)₂Re(CO)₂]Cl (5), and [(o-Ph₂PC₆H₄NH₂)₂Re- (CO)₂]Cl (6), were applied for the first time in homogeneous catalytic hydrogenation of ketones to alcohols. Complexes with one PN ligand (1~3) and two PN ligands (4~6) exhibited comparable catalytic performance. Using optimal complex 2, the important factors with significant influences on the catalytic activity were well optimized, including the loading of catalyst, additive, temperature, and so on. Under suitable conditions, complex 2 effectively hydrogenated nearly 30 diverse ketones to their corresponding alcohols.

Key words: rhenium complex, bidentate PN ligand, catalytic hydrogenation, ketone

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Fang Xiaolong, Wang Jun, Xu Shuting, Li Hao, Hu Kun, Chen, Yiyu. Efficient Hydrogenation of Ketones to Alcohols Catalysed by Phosphinoamine Rhenium Complexes[J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 241-249.

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Fig. & Tab. 7

Figure 1. Representative rhenium catalysts bearing PNP-pincer ligand for hydrogenation reactions

Figure 2. Structures of rhenium complexes 1~6

Figure 3. X-ray crystal structures of rhenium complexes 2 (a), 3 (b) and 5 (c)

Figure 4. Catalytic hydrogenation of acetophenone to 1-phenyl- ethanol by rhenium complexes 1~6 Reaction condition: 2.0 mmol of acetophenone (0.5 mmol/mL i-PrOH solution), 0.1 mol% Re complex, 10 mol% NaOEt, 2 MPa of H2, 100 ℃, 4 h

Entry	2/mol%	Temp./ ℃	p(H₂)/ MPa	Time/h	Yield^b/ %	TOF/ h^－1	TON
1	0.1	100	2	1	80	803	803
2	0.1	100	2	4	94	236	942
3	0.1	120	2	1	>99	999	999
4	0.1	100	1	4	90	226	904
5	0.1	80	2	8	64	80	636
6	0.1	80	1	8	62	78	624
7^c	0.1	100	2	4	10	26	104
8^d	0.1	100	2	4	52	130	518
9^e	0.1	100	2	4	81	203	812
10^f	0.01	100	5	12	>99	833	9990
11^g	0.002	120	5	12	50	2079	24950
12^h	0.001	120	5	12	42	3500	42000

Table 1. Catalytic hydrogenation of acetophenone to 1-phenyl- ethanol by 2

Table 2. Catalytic hydrogenation of ketones to alcohols by 2

Figure 5. Proposed reaction mechanism for the hydrogenation of acetophenone to 1-phenylethanol by 2

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膦胺铼配合物催化酮加氢制醇性能研究

Efficient Hydrogenation of Ketones to Alcohols Catalysed by Phosphinoamine Rhenium Complexes

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