Efficient Hydrogenation of Ketones to Alcohols Catalysed by Phosphinoamine Rhenium Complexes

doi:10.6023/cjoc202506024

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

Cite this article

Xiaolong Fang, Jun Wang, Shuting Xu, Hao Li, Kun Hu, 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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