非均相催化氢甲酰化的串联反应研究进展

doi:10.6023/cjoc202405034

摘要/Abstract

氢甲酰化反应是工业上合成醛的重要方法之一. 醛进一步通过有机反应转化为缩醛、醇、胺和羧酸等多种精细化学品. 随着绿色化学的发展, 非均相催化剂由于分离和循环使用等优势而引起广泛的关注. 另外, 基于氢甲酰化的串联反应能够“一锅法”得到醛的衍生物, 不需要分离中间体醛, 减少反应步骤和能量消耗, 进而有效地提高了催化效率. 因此, 结合非均相催化和串联反应的理念, 发展非均相的氢甲酰化串联反应催化剂具有重要的研究价值. 此综述总结了非均相氢甲酰化-缩醛化、氢甲酰化-氢化、氢胺甲基化和氢甲酰化-Aldol四类串联反应的研究进展, 介绍了催化剂的合成及应用. 最后, 对催化剂的发展和反应方向进了展望.

关键词: 非均相催化剂, 氢甲酰化-缩醛化, 氢甲酰化-氢化, 氢胺甲基化, 氢甲酰化-Aldol

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

引用此文

周宇飞, 贾肖飞. 非均相催化氢甲酰化的串联反应研究进展[J]. 有机化学, 2024, 44(10): 3147-3158.

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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[1]	Roelen, O. DE 849548, 1938.
[2]	(a) Franke, R.; Selent, D.; Börner, A. Chem. Rev. 2012, 112, 5675.
	(b) Zhao, K.; Wang, X.; He, D.; Wang, H.; Qian, B.; Shi, F. Catal. Sci. Technol. 2022, 12, 4962.
	(c) Chakrabortty, S.; Almasalma, A. A.; de Vries, J. G. Catal. Sci. Technol. 2021, 11, 5388.
	(d) Pospech, J.; Fleischer, I.; Franke, R.; Buchholz, S.; Beller, M. Angew. Chem., Int. Ed. 2013, 52, 2852.
	(e) Jia, X.; Wang, Z.; Xia, C.; Ding, K. Chin. J. Org. Chem. 2013, 33, 1369. (in Chinese)
	(贾肖飞, 王正, 夏春谷, 丁奎岭, 有机化学, 2013, 33, 1369.) doi: 10.6023/cjoc201304005
	(f) Li, S.; Li, Z.; You, C.; Lv, H.; Zhang, X. Chin. J. Org. Chem. 2019, 39, 1568. (in Chinese)
	(李帅龙, 李庄星, 由才, 吕辉, 张绪穆, 有机化学, 2019, 39, 1568.)
	(g) Zhang, J.; Sun, P.; Gao, G.; Wang, J.; Zhao, Z.; Muhammad, Y.; Li, F. J. Catal. 2020, 387, 196.
[3]	(a) Bondžić, B. P. J. Mol. Catal. A: Chem. 2015, 408, 310. pmid: 11749518
	(b) Behr, A.; Vorholt, A. J.; Ostrowski, K. A.; Seidensticker, T. Green Chem. 2014, 16, 982. pmid: 11749518
	(c) Vasylyev, M.; Alper, H. Synthesis 2010, 17, 2893. pmid: 11749518
	(d) Rodrigues, F. M. S.; Carrilho, R. M. B.; Pereira, M. M. Eur. J. Inorg. Chem. 2021, 24, 2294. pmid: 11749518
	(e) Eilbracht, P.; Barfacker, L.; Buss, C.; Hollmann, C.; Kitsos- Rzychon, B. E.; Kranemann, C. L.; Rische, T.; Roggenbuck, R.; Schmidt, A. Chem. Rev. 1999, 99, 3329. pmid: 11749518
[4]	(a) Gao, W.; Liu, S.; Wang, Z.; Peng, J.; Zhang, Y.; Yuan, X.; Zhang, X.; Li, Y.; Pan, Y. Energy Fuels 2024, 38, 2526. pmid: 29657887
	(b) Liu, B.; Wang, Y.; Huang, N.; Lan, X.; Xie, Z.; Chen, J. G.; Wang, T. Chem 2022, 8, 2630. pmid: 29657887
	(c) Zong, L.; Chen, J.; Ren, X.; Zhang, G.; Jia, X. Chin. J. Org. Chem. 2020, 40, 2308. (in Chinese) pmid: 29657887
	(宗玲博, 陈建宾, 任新意, 张国营, 贾肖飞, 有机化学, 2020, 40, 2308.) doi: 10.6023/cjoc202003006 pmid: 29657887
	(d) Nurttila, S. S.; Linnebank, P. R.; Krachko, T.; Reek, J. N. H. ACS Catal. 2018, 8, 3469. doi: 10.1021/acscatal.8b00288 pmid: 29657887
	(e) Li, C. Y.; Wang, W. L.; Yan, L.; Ding, Y. J. Front. Chem. Sci. Eng. 2018, 12, 113. pmid: 29657887
[5]	Torres, G. M.; Frauenlob, R.; Franke, R.; Börner, A. Catal. Sci. Technol. 2015, 5, 34.
[6]	(a) Kalck, P.; Urrutigoïty, M. Chem. Rev. 2018, 118, 3833.
	(b) Chen, C.; Dong, X.-Q.; Zhang, X. Org. Chem. Front. 2016, 3, 1359.
	(c) Crozet, D.; Urrutigoty, M.; Kalck, P. ChemCatChem 2011, 3, 1102.
	(d) Monciatti, E.; Migliorini, F.; Romagnoli, G.; Vogt, M.; Langer, R.; Parisi, M. L.; Petricci, E. ACS Sustainable Chem. Eng. 2023, 11, 13387.
[7]	(a) Gäumann, P.; Rohrbach, T.; Artiglia, L.; Ongari, D.; Smit, B.; van Bokhoven, J. A.; Ranocchiari, M. Chem. Eur. J. 2023, 6, e202300939.
	(b) Fang, X.; Jackstell, R.; Börner, A.; Beller, M. Chem. Eur. J. 2014, 20, 15692.
[8]	Chercheja, S.; Rothenbücher, T.; Eilbracht, P. Adv. Synth. Catal. 2009, 351, 339.
[9]	Fuchs, D.; Nasr-Esfahani, M.; Diab, L.; Šmejkal, T.; Breit, B. Synlett 2013, 24, 1657.
[10]	(a) Climent, M. J.; Velty, A.; Corma, A. Green Chem. 2002, 4, 565.
	(b) Gorbunov, D. N.; Shchukina, T. V.; Kardasheva, Y. S.; Sinikova, N. A.; Maksimov, A. L.; Karakhanov, E. A. Pet. Chem. 2016, 56, 711.
	(c) Shu, Z.; Zhao, X.-X.; Zheng, Z.; Zhang, X.; Zhang, Y.; Sun, S.; Chen, J.; Xie, C.; Yuan, B.; Jia, X. Chem. Commun. 2023, 59, 5237.
[11]	Jin, X.; Zhao, K.; Cui, F.; Kong, F.; Liu, Q. Green Chem. 2013, 15, 3236.
[12]	Norinder, J.; Rodrigues, C.; Börner, A. J. Mol. Catal. A: Chem. 2014, 391, 139.
[13]	(a) Li, Y.-Q.; Wang, P.; Liu, H.; Lu, Y.; Zhao, X.-L.; Liu, Y. Green Chem. 2016, 18, 1798.
	(b) Yang, D.; Zhang, L.; Liu, H.; Yang, C. Acta Chim. Sinica 2021, 79, 658. (in Chinese) doi: 10.6023/A21010005
	(杨妲, 张龙力, 刘欢, 杨朝合, 化学学报, 2021, 79, 658.) doi: 10.6023/A21010005
[14]	Wang, P.; Chen, X.; Wang, D.-L.; Li, Y.-Q.; Liu, Y. Green Energy Environ. 2017, 2, 419.
[15]	Liu, H.; Liu, L.; Guo, W.-D.; Lu, Y.; Zhao, X.-L.; Liu, Y. J. Catal. 2019, 373, 215.
[16]	(a) Gorbunov, D.; Nenasheva, M.; Gorbunov, A.; Matsukevich, R.; Maximov, A.; Karakhanov, E. React. Chem. Eng. 2021, 6, 839.
	(b) Gorbunov, D. N.; Nenasheva, M. V.; Sinikova, N. A.; Kardasheva, Y. S.; Maksimov, A. L.; Karakhanov, E. A. Russ. J. Appl. Chem. 2018, 91, 990.
[17]	Ali, B. E.; Tijani, J.; Fettouhi, M. Appl. Catal. A 2006, 303, 213.
[18]	Li, X.; Qin, T.; Li, L.; Wu, B.; Lin, T.; Zhong, L. Catal. Lett. 2021, 151, 2638.
[19]	Singh, A. S.; Kachgunde, H. G.; Ravi, K.; Naikwadi, D. R.; Biradar, A. V. Mol. Catal. 2024, 555, 113859.
[20]	(a) Liang, Z.; Chen, J.; Chen, X.; Zhang, K.; Lv, J.; Zhao, H.; Zhang, G.; Xie, C.; Zong, L.; Jia, X. Chem. Commun. 2019, 55, 13721.
	(b) Jia, X.; Liang, Z.; Chen, J.; Lv, J.; Zhang, K.; Gao, M.; Zong, L.; Xie, C. Org. Lett. 2019, 21, 2147.
	(c) Zhang, J.; Li, J.; Li, K.; Zhao, J.; Yang, Z.; Zong, L.; Chen, J.; Xie, C.-X.; Zhao, X.-X.; Jia, X. Catal. Sci. Technol. 2022, 12, 3440.
[21]	Shu, Z.; Zhang, X.; Meng, W.; Yu, Z.; Zhou, Y.; Chen, C.; Yuan, B.; Jia, X. ACS Sustainable Chem. Eng. 2024, 12, 2430.
[22]	Balué, J.; Bayón, J. C. J. Mol. Catal. A: Chem. 1999, 137, 193.
[23]	Carvalho, G. A.; Gusevskaya, E. V.; dos Santos, E. N. J. Braz. Chem. Soc. 2014, 25, 2370.
[24]	(a) Hunter, D. L.; Moore, S. E. Appl. Catal. 1985, 19, 259.
	(b) Hunter, D. L.; Moore, S. E. Appl. Catal. 1985, 19, 275.
[25]	Alvila, L.; Pakkanen, T. A.; Pakkanen, T. T. J. Mol. Catal. 1992, 71, 281.
[26]	Corain, B.; Basato, M.; Zecca, M. J. Mol. Catal. 1992, 73, 23.
[27]	Alvila, L.; Pakkanen, T. A.; Pakkanen, T. T. J. Mol. Catal. A: Chem. 1995, 102, 79.
[28]	Ma, Y.; Qing, S.; Gao, Z.; Mamat, X.; Zhang, J.; Li, H.; Eli, W.; Wang, T. Catal. Sci. Technol. 2015, 5, 3649.
[29]	Bhagade, S. S.; Chaurasia, S. R.; Bhanage, B. M. Catal. Today 2018, 309, 147.
[30]	Oseghale, C. O.; Mogudi, B. M.; Akinnawo, C. A.; Meijboom, R.; Appl. Catal. A, Gen. 2020, 602, 117735.
[31]	Gorbunov, D.; Nenasheva, M.; Naranov, E.; Maximov, A.; Rosenberg, E.; Karakhanov, E. Appl. Catal. A, Gen. 2021, 623, 118266.
[32]	Shi, Y.; Li, J.; Shen, X.; Xie, P.; Gong, J.; Sun, H.; Hu, X.; Zhu, B.; Huang, W. ChemPhysChem 2023, 24, e202200910.
[33]	(a) Ahlers, S. J.; Kraehnert, R.; Kreyenschulte, C.; Pohl, M.-M.; Linke, D.; Kondratenko, E. V. Catal. Today 2015, 258, 684.
	(b) Ahlers, S. J.; Pohl, M.-M.; Radnik, J.; Linke, D.; Kondratenko, E. V. Appl. Catal. B, Environ. 2015, 176-177, 570.
[34]	Mavlyankariev, S. A.; Ahlers, S. J.; Kondratenko, V. A.; Linke, D.; Kondratenko, E. V. ACS Catal. 2016, 6, 3317.
[35]	Heyl, D.; Kreyenschulte, C.; Kondratenko, V. A.; Bentrup, U.; Kondratenko, E. V., Brückner, A. ChemSusChem 2019, 12, 651.
[36]	Nenasheva, M.; Gorbunov, D.; Karasaeva, M.; Maximov, A.; Karakhanov, E. Mol. Catal. 2021, 516, 112010.
[37]	Püschel, S.; Hammami, E.; Rösler, T.; Ehmann, K. R.; Vorholt, A. J.; Leitner, W. Catal. Sci. Technol. 2022, 12, 728.
[38]	Wang, Y. Y.; Luo, M. M.; Lin, Q.; Chen, H.; Li, X. J. Green Chem. 2006, 8, 545.
[39]	Hamers, B.; Baeuerlein, P. S.; Muller, C.; Vogt, D. Adv. Synth. Catal. 2008, 350, 332.
[40]	Schneider, M. J.; Lijewski, M.; Woelfel, R.; Haumann, M.; Wasserscheid, P. Angew. Chem., Int. Ed. 2013, 52, 6996.
[41]	Zimmermann, B.; Herwig, J.; Beller, M. Angew. Chem., Int. Ed. 1999, 38, 2372.
[42]	Wang, Y. Y.; Luo, M. M.; Li, Y. Z.; Chen, H.; Li, X. J. Appl. Catal., A 2004, 272, 151.
[43]	Wang, Y. Y.; Chen, J. H.; Luo, M. M.; Chen, H.; Li, X. J. Catal. Commun. 2006, 7, 979.
[44]	Behr, A.; Becker, M.; Reyer, S. Tetrahedron Lett. 2010, 51, 2438.
[45]	Faßbach, T. A.; Sommer, F. O.; Vorholt, A. J. Adv. Synth. Catal. 2018, 360, 1473.
[46]	Jagtap, S. A.; Gowalkar, S. P.; Monflier, E.; Ponchel, A.; Bhanage, B. M. Mol. Catal. 2018, 452, 108.
[47]	Zhang, L.; Ning, Y.; Ye, B.; Ru, T.; Chen, F.-E. Green Chem. 2022, 24, 4420.
[48]	Dutta, B.; Schwarz, R.; Omar, S.; Natour, S.; Abu-Reziq, R. Eur. J. Org. Chem. 2015, 1961.
[49]	An, J.; Gao, Z.; Wang, Y.; Zhang, Z.; Zhang, J.; Li, L.; Tang, B.; Wang, F. Green Chem. 2021, 23, 2722.
[50]	Zhao, K.; Wang, H.; Wang, X.; Cui, X.; Shi, F. Chem. Commun. 2022, 58, 8093.
[51]	Qian, C.; Zheng, Q.; Chen, J.; Tu, B.; Tu, T. Green Chem. 2023, 25, 1368.
[52]	Strohmann, M.; Vossen, J. T.; Vorholt, A. J.; Leitner, W. Green Chem. 2020, 22, 8444.
[53]	(a) Peng, J.-B.; Geng, H.-Q.; Wu, X.-F. Chem 2019, 5, 526.
	(b) An, D.-L.; Bao, Z.-P.; Wu, X.-F. Chin. J. Org. Chem. 2023, 43, 2304. (in Chinese)
	(安大列, 包志鹏, 吴小锋, 有机化学, 2023, 43, 2304.) doi: 10.6023/cjoc202301010
	(c) Liu, Y.; Chen, Y.-H.; Yi, H.; Lei, A. ACS Catal. 2022, 12, 7470.
	(d) Wang, P.; Yang, D.; Liu, H. Chin. J. Org. Chem. 2021, 41, 3379. (in Chinese)
	(王鹏, 杨妲, 刘欢, 有机化学, 2021, 41, 3379.)
	(e) Yang, L.; Shi, L.; Xia, C.; Li, F. Chin. J. Chem. 2020, 41, 1152.
	(f) Shi, L.; Wen, M.; Li, F. Chin. J. Chem. 2020, 39, 317.
	(g) Shi, H.; Wang, Y.; Wang, P.; Zhao, D.; Feng, B.; Yan, Y.; Yang, G. Chin. J. Org. Chem. 2024, 44, 1811. (in Chinese)
	(史会兵, 王耀伟, 王鹏, 赵德明, 冯保林, 晏耀宗, 杨桂爱, 有机化学, 2024, 44, 1811.) doi: 10.6023/cjoc202301025
	(h) Yang, Z.; Shen, C.; Dong, K. Chin. J. Chem. 2022, 40, 2734.
[54]	Li, X.; You, C.; Yang, J.; Li, S.; Zhang, D.; Lv, H.; Zhang, X. Angew. Chem., Int. Ed. 2019, 58, 10928.
[55]	(a) Chen, C.; Jin, S.; Zhang, Z.; Wei, B.; Wang, H.; Zhang, K.; Lv, H.; Dong, X.-Q.; Zhang, X. J. Am. Chem. Soc. 2016, 138, 9017.
	(b) Li, S.; Li, Z.; Li, M.; He, L.; Zhang, X.; Lv, H. Nat. Commun. 2021, 12, 5279.
	(c) You, C.; Li, S.; Li, X.; Lv, H.; Zhang, X. ACS Catal. 2019, 9, 8529.
[56]	Samanta, P.; Canivet, J. ChemCatChem 2024, 16, e202301435.
[57]	(a) Liu, Y.; Dikhtiarenko, A.; Xu, N.; Sun, Ji.; Tang, J.; Wang, K.; Xu, B.; Tong, Q.; Heeres, H. J.; He, S.; Gascon, J.; Fan, Y. Chem. Eur. J. 2020, 26, 12134.
	(b) Pilaski, M.; Artz, J.; Islam, H.-U.; Beale, A. M.; Palkovits, R. Microporous Mesoporous Mater. 2016, 227, 219.
[58]	(a) Kramer, S.; Bennedsen, N. R.; Kegnæs, S. ACS Catal. 2018, 8, 6961. pmid: 26505055
	(b) Kathiresan, M. Chem.-Asian J. 2023, 18, e202201299. pmid: 26505055
	(c) Sun, Q.; Dai, Z.; Meng, X.; Xiao, F.-S. Chem. Soc. Rev. 2015, 44, 6018. pmid: 26505055
	(d) Yue, C.; Xing, Q.; Sun, P.; Zhao, Z.; Lv, H.; Li, F. Nat. Commun. 2021, 12, 1875. pmid: 26505055
	(e) Lv, H.; Wang, W.; Li, F. Chem. Eur. J. 2018, 24, 16588. pmid: 26505055

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]