Progress in Heterogeneous Catalyzed Tandem Reactions Based on Hydroformylation

doi:10.6023/cjoc202405034

Abstract

Hydroformylation is one of the most important methods to synthesize aldehydes in industry. Aldehydes are converted into various fine chemicals such as acetals, alcohols, amines and carboxylic acids by further organic reactions. With the development of green chemistry, heterogeneous catalysts have attracted wide attention due to their advantages of easy separation and recycling. In addition, the tandem reaction based on hydroformylation can afford aldehyde derivatives by one-pot method reaction, without separating the intermediate aldehyde products, reducing the reaction steps and energy consumption, and effectively improving the catalytic efficiency. Therefore, combining the concept of heterogeneous catalysis and tandem reaction, the development of heterogeneous catalyst for hydroformylation related tandem reaction has important research value. The research progress of heterogeneous tandem hydroformylation-acetalization, hydroformylation-hydrogena- tion, hydroaminomethylation and hydroformylation-aldol is summarized, including the synthesis and application of catalysts. Finally, development of catalyst and tandem reaction are prospected.

Key words: heterogeneous catalysts, hydroformylation-acetalization, hydroformylation-hydrogenation, hydroaminomethyla- tion, hydroformylation-Aldol

Cite this article

Yufei Zhou, Xiaofei Jia. Progress in Heterogeneous Catalyzed Tandem Reactions Based on Hydroformylation[J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3147-3158.

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Entry	Catalyst	Substrate	Reaction condition	Yield/%	n∶i	Ref.
1	Rh-[L1•H][BF₄]	1-Octene, CH₃OH	[bmim][BF₄], p(H₂/CO, V/V=1/1)=5.0 MPa, 80 ℃, 2 h, S/C=1000	91	3.0	[11]
2	Ru₃(CO)₁₂	1-Octene, glycol	[bmim][BF₄], HOAc, p(H₂/CO, V/V=1/1)=2.0 MPa, 140 ℃, 20 h, S/C=149	87	1.0	[12]
3	Rh(acac)(CO)₂/L2	1-Octene, CH₃OH	[bmim][BF₄], p(H₂/CO, V/V=1/1)=4.0 MPa, 120 ℃, 2 h, S/C=2000	82	1.9	[13a]
4	[Ir(COD)Cl]₂/L₂	1-Octene, CH₃OH	NMP, p(H₂/CO, V/V=1/4)=4.0 MPa, 120 ℃, 8 h, S/C=200	84	3.9	[13b]
5	Rh(acac)(CO)₂/ dppb-Q	1-Octene, CH₃OH	dppb-DQ, p(H₂/CO, V/V=1/1)=4.0 MPa, 100 ℃, 3 h, S/C=1000	92	1.2	[14]
6	L3-IrCl₃•3H₂O	1-Hexene, CH₃OH	[Bmim]PF_6,p(H₂/CO, V/V=1/5)=4.0 MPa, 110 ℃, 15 h, S/C=500	89	3.5	[15]
7	RhCl₃/TPPTS	Ethylene, glycol	Toluene/H₂O, H₂SO₄, p(H₂/CO, V/V=1/1)=6.0 MPa, 90 ℃, 2 h, S/C=1611	89	—	[16]
8	Rh32MCM-M	Styrene, CH₃OH	H₃PW₁₂O₄₀, p(H₂/CO, V/V=1/5)=4.1 MPa, 80 ℃, 6 h, S/C=847	77	1∶7	[17]
9	Rh/SiO₂	1-Hexene, CH₃OH	p(H₂/CO, V/V=1/1)=4.0 MPa, 120 ℃, 8 h, S/C=575	95	0.8	[18]
10	Rh@ZrP	Styrene, glycol	p(H₂/CO, V/V=1/1)=3.0 MPa, 80 ℃, 6 h, S/C=247	99	1.9	[19]
11	Rh/POP-BINAPa& PPh₃@ZSM-35(10)	1-Hexene, CH₃OH	p(H₂/CO, V/V=1/1)=2.0 MPa, 120 ℃, 24 h, S/C=10000	97	87.8	[21]
12	Cat.1	Styrene, CH₃OH	p(H₂/CO, V/V=1/1)=0.8 MPa, 80 ℃, 16 h, S/C=200	87	0.18	[22]
13	IRA900/TPPMS/Rh	Eugenol, CH₃OH	p(H₂/CO, V/V=1/1)=6.0 MPa, 70 ℃, 24 h, S/C=556	89	1.6	[23]

Entry	Catalyst	Substrate	Reaction condition	Yield/%	n∶i	Ref.
1	Rh-[L1•H][BF₄]	1-Octene, CH₃OH	[bmim][BF₄], p(H₂/CO, V/V=1/1)=5.0 MPa, 80 ℃, 2 h, S/C=1000	91	3.0	[11]
2	Ru₃(CO)₁₂	1-Octene, glycol	[bmim][BF₄], HOAc, p(H₂/CO, V/V=1/1)=2.0 MPa, 140 ℃, 20 h, S/C=149	87	1.0	[12]
3	Rh(acac)(CO)₂/L2	1-Octene, CH₃OH	[bmim][BF₄], p(H₂/CO, V/V=1/1)=4.0 MPa, 120 ℃, 2 h, S/C=2000	82	1.9	[13a]
4	[Ir(COD)Cl]₂/L₂	1-Octene, CH₃OH	NMP, p(H₂/CO, V/V=1/4)=4.0 MPa, 120 ℃, 8 h, S/C=200	84	3.9	[13b]
5	Rh(acac)(CO)₂/ dppb-Q	1-Octene, CH₃OH	dppb-DQ, p(H₂/CO, V/V=1/1)=4.0 MPa, 100 ℃, 3 h, S/C=1000	92	1.2	[14]
6	L3-IrCl₃•3H₂O	1-Hexene, CH₃OH	[Bmim]PF_6,p(H₂/CO, V/V=1/5)=4.0 MPa, 110 ℃, 15 h, S/C=500	89	3.5	[15]
7	RhCl₃/TPPTS	Ethylene, glycol	Toluene/H₂O, H₂SO₄, p(H₂/CO, V/V=1/1)=6.0 MPa, 90 ℃, 2 h, S/C=1611	89	—	[16]
8	Rh32MCM-M	Styrene, CH₃OH	H₃PW₁₂O₄₀, p(H₂/CO, V/V=1/5)=4.1 MPa, 80 ℃, 6 h, S/C=847	77	1∶7	[17]
9	Rh/SiO₂	1-Hexene, CH₃OH	p(H₂/CO, V/V=1/1)=4.0 MPa, 120 ℃, 8 h, S/C=575	95	0.8	[18]
10	Rh@ZrP	Styrene, glycol	p(H₂/CO, V/V=1/1)=3.0 MPa, 80 ℃, 6 h, S/C=247	99	1.9	[19]
11	Rh/POP-BINAPa& PPh₃@ZSM-35(10)	1-Hexene, CH₃OH	p(H₂/CO, V/V=1/1)=2.0 MPa, 120 ℃, 24 h, S/C=10000	97	87.8	[21]
12	Cat.1	Styrene, CH₃OH	p(H₂/CO, V/V=1/1)=0.8 MPa, 80 ℃, 16 h, S/C=200	87	0.18	[22]
13	IRA900/TPPMS/Rh	Eugenol, CH₃OH	p(H₂/CO, V/V=1/1)=6.0 MPa, 70 ℃, 24 h, S/C=556	89	1.6	[23]

Entry	Catalyst	Substrate	Reaction condition	Yield/%	n∶i	Ref.
1	Rh/MWA-1	Dicyclopentadiene	Toluene/THF (V/V=5/1), p(H₂/CO, V/V=2/1)=27.6 MPa, 130 ℃, S/C=405	94	—	[24]
2	Rh/Co/MWA-1	1-Hexene	Toluene, p(H₂/CO, V/V=1/1)=5 MPa, 100 ℃, 17 h, S/C_Rh=447	99	1.1	[25]
3	CO₂Rh₂(CO)₁₂-Al₂O₃	1-Hexene	Toluene, Et₃N, p(H₂/CO, V/V=1/1)=5 MPa, 100 ℃, 17 h, S/C=296	97	0.9	[27]
4	Au/Co₃O₄	Dicyclopentadiene	THF, PPh₃, p(H₂/CO, V/V=1/1)=7~9 MPa, 140 ℃, 6 h	90	—	[28]
5	Co₃O₄	1-Octene	THF, Et₃N, p(H₂/CO, V/V=2/1)=5.5 MPa, 150 ℃, 12 h, S/C=16.7	93	2.3	[29]
6	Au/Cs-Co₃O₄	1-Octene	THF, p(H₂/CO, V/V=1/2)=4 MPa, 140 ℃, 16 h	87	2.3	[30]
7	Rh/BP-1-NMe₂	1-Octene	Toluene, p(H₂/CO, V/V=3/1)=6 MPa, 80 ℃, 12 h, S/C=600	92	1	[31]
8	Rh-Co/g-CN	Styrene	Toluene, p(H₂/CO, V/V=1/1)=6 MPa, 100~170 ℃, 16 h, S/C_Rh=2871	89	0.9	[32]
9	Rh/(CH₂CH₂OH)₃N	1-Hexene	Dodecane, p(H₂/CO, V/V=1/1,)=6 MPa, 90 ℃, 8 h, S/C_Rh=500.	42	1.2	[36]
10	Rh/DMAE	1-Octene	H₂O, p(H₂/CO, V/V=1/2)=6 MPa, 100 ℃, 1.5 h, S/C=200	64	—	[37]

Entry	Catalyst	Substrate	Reaction condition	Yield/%	n∶i	Ref.
1	Rh/MWA-1	Dicyclopentadiene	Toluene/THF (V/V=5/1), p(H₂/CO, V/V=2/1)=27.6 MPa, 130 ℃, S/C=405	94	—	[24]
2	Rh/Co/MWA-1	1-Hexene	Toluene, p(H₂/CO, V/V=1/1)=5 MPa, 100 ℃, 17 h, S/C_Rh=447	99	1.1	[25]
3	CO₂Rh₂(CO)₁₂-Al₂O₃	1-Hexene	Toluene, Et₃N, p(H₂/CO, V/V=1/1)=5 MPa, 100 ℃, 17 h, S/C=296	97	0.9	[27]
4	Au/Co₃O₄	Dicyclopentadiene	THF, PPh₃, p(H₂/CO, V/V=1/1)=7~9 MPa, 140 ℃, 6 h	90	—	[28]
5	Co₃O₄	1-Octene	THF, Et₃N, p(H₂/CO, V/V=2/1)=5.5 MPa, 150 ℃, 12 h, S/C=16.7	93	2.3	[29]
6	Au/Cs-Co₃O₄	1-Octene	THF, p(H₂/CO, V/V=1/2)=4 MPa, 140 ℃, 16 h	87	2.3	[30]
7	Rh/BP-1-NMe₂	1-Octene	Toluene, p(H₂/CO, V/V=3/1)=6 MPa, 80 ℃, 12 h, S/C=600	92	1	[31]
8	Rh-Co/g-CN	Styrene	Toluene, p(H₂/CO, V/V=1/1)=6 MPa, 100~170 ℃, 16 h, S/C_Rh=2871	89	0.9	[32]
9	Rh/(CH₂CH₂OH)₃N	1-Hexene	Dodecane, p(H₂/CO, V/V=1/1,)=6 MPa, 90 ℃, 8 h, S/C_Rh=500.	42	1.2	[36]
10	Rh/DMAE	1-Octene	H₂O, p(H₂/CO, V/V=1/2)=6 MPa, 100 ℃, 1.5 h, S/C=200	64	—	[37]

Entry	Catalyst	Substrate	Reaction condition	Yield/%	n∶i	Ref.
1	Rh/BISBIS	1-Octene, morpholine	[BMIM][p-CH₃C₆H₄SO₃], p(H₂/CO, V/V=1∶1)=3.0 MPa, 130 ℃, 5 h, S/C=500	81	21.4	[38]
2	Rh/sulfoxantphos	1-Octene, piperidine	[PMIM][BF₄], p(H₂/CO, V/V=1∶2)=3.6 MPa, 125 ℃, 17 h, S/C=4000	92	27.7	[39]
3	Rh/Ir/BINAS	Acrylic, NH₃•H₂O	MTBE/H₂O, p(H₂/CO, V/V=5∶1)=7.8 MPa, 130 ℃, 10 h, S/C_Rh=3846, S/C_Ir=476	90	99	[41]
4	Rh/TPPTS	1-Octene, dimethylamine	H₂O, CTAB, p(H₂/CO, V/V=1∶1)=3 MPa, 130 ℃, 5 h	41	9.6	[42]
5	Rh/BISBIS	Dodecene, dimethylamine	H₂O, CTAB, p(H₂/CO, V/V=1∶1)=3 MPa, 130 ℃, 5 h	78.4	70.3	[43]
6	Rh/Sulfoxantphos	1-Octene, diethanolamine	1-BuOH/H₂O, p(H₂/CO, V/V=3∶1)=5 MPa, 100 ℃, 8 h, S/C=769	79	—	[45]
7	Rh/TPPTS/ RAME-β-CD	Eugenol, cyclohexylamine	H₂O, p(H₂/CO, V/V=3∶1)=3 MPa, 80 ℃, 6 h, S/C=500	81	9	[46]
8	Rh/L4	Styrene, aniline	H₂O, p(H₂/CO, V/V=3∶1)=3 MPa, 60 ℃, 24 h, S/C=200	82	0.01	[47]
9	Rh/MNP-NHC	Styrene, morpholine	CH₂Cl₂, p(H₂/CO, V/V=1∶1)=6.9 MPa, 80 ℃, 16 h, S/C=500	98	0.06	[48]
10	Ru/TiO₂	Cyclohexene, cyclohexylamine	THF, p(H₂/CO, V/V=1/1)=1.0 MPa, 160 ℃, 12 h, S/C_Rh=51	85	—	[49]
11	Rh@CPOL-DPMphos&p-3vPPh₃	1-Octene, N-methylaniline	CH₃OH, TsOH•H₂O, P (H₂/CO, V/V=1/1)=2.0 MPa, 120 ℃, 24 h, S/C=1000	90	5.7	[50]
12	NHC-Rh	Phenylpropene, N-methylaniline	THF, P (H₂/CO, V/V=9/1)=8.0 MPa, 150 ℃, 18 h, S/C=100	95	32.3	[51]

非均相催化氢甲酰化的串联反应研究进展