Highly efficient upgrading of 1-butanol into 2‐ethyl‐1‐hexanol catalyzed by nickel pincer complexes

doi:10.1016/S1872-2067(26)64997-2

Abstract

Abstract:

The Guerbet reaction of biomass-derived 1-butanol offers a sustainable route to valuable 2-ethyl-1-hexanol (2-EH), yet faces significant challenges, including low conversions, poor selectivity and reliance on noble metal catalysts and additional solvents. Herein, we report a highly efficient nickel pincer-catalyzed system that achieves new records of 86% 1-butanol conversion and 80% 2-EH yield. This constitutes the first homogeneous non-noble metal catalyst for 1-butanol upgrading to higher alcohols with both high conversion and high TON. Furthermore, the protocol demonstrates broad applicability, enabling selective valorization of diverse alcohol feedstocks to their elongated counterparts.

Key words: 1-Butanol upgrading, Nickel pincer complex, 2‐Ethyl‐1‐hexanol, Guerbet process, Homogeneous catalysis

Xintao Zhu, Qiuling Xia, Yue Hu, Yinjun Xie. Highly efficient upgrading of 1-butanol into 2‐ethyl‐1‐hexanol catalyzed by nickel pincer complexes[J]. Chinese Journal of Catalysis, 2026, 84: 368-374.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64997-2

https://www.cjcatal.com/EN/Y2026/V84/I5/368

Figures/Tables 7

References

[1]	H. Bahrmann, H.-D. Hahn, D. Mayer, G. D. Frey, Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2013.
[2]	L. Zhao, Y. Wang, H. An, X. Zhao, Y. Wang, Catal. Commun., 2018, 103, 74-77.
[3]	G. M. Torres, R. Frauenlob, R. Franke, A. Börner, Catal. Sci. Technol., 2015, 5, 34-54.
[4]	N. Liang, X. Zhang, H. An, X. Zhao, Y. Wang, Green Chem., 2015, 17, 2959-2972.
[5]	W. Li, Y. Yang, H. Zhang, Y. Fang, ChemSusChem, 2025, 18, e202400899.
[6]	P. Anbarasan, Z. C. Baer, S. Sreekumar, E. Gross, J. B. Binder, H. W. Blanch, D. S. Clark, F. D. Toste, Nature, 2012, 491, 235-239.
[7]	C. Jin, M. Yao, H. Liu, C. F. Lee, J. Ji, Renewable Sustain. Energy Rev., 2011, 15, 4080-4106.
[8]	C. Weizmann, GB 191504845 A, 1919.
[9]	B. G. Reed-Berendt, D. E. Latham, M. B. Dambatta, L. C. Morrill, ACS Cent. Sci., 2021, 7, 570-585.
[10]	T. Irrgang, R. Kempe, Chem. Rev., 2019, 119, 2524-2549.
[11]	A. Corma, J. Navas, M. J. Sabater, Chem. Rev., 2018, 118, 1410-1459.
[12]	Q. Yang, Q. Wang, Z. Yu, Chem. Soc. Rev., 2015, 44, 2305-2329.
[13]	Y. Gao, G. Hong, B.-M. Yang, Y. Zhao, Chem. Soc. Rev., 2023, 52, 5541-5562.
[14]	A. M. Davies, Z.-Y. Li, C. R. J. Stephenson, N. K. Szymczak, ACS Catal., 2022, 12, 6729-6736.
[15]	A. J. O’Lenick Jr, J. Surfactants Deterg., 2001, 4, 311-315.
[16]	S. Veibel, J. I. Nielsen, Tetrahedron, 1967, 23, 1723-1733.
[17]	M. Guerbet, C. R. Acad. Sci. Paris, 1909, 149, 129-132.
[18]	M. Guerbet, C. R. Acad. Sci. Paris, 1899, 128, 1002-1004.
[19]	M. Biermann, H. Gruß, W. Hummel, H. Gröger, ChemCatChem, 2016, 8, 895-899.
[20]	D. Gabriëls, W. Y. Hernández, B. Sels, P. Van Der Voort, A. Verberckmoes, Catal. Sci. Technol., 2015, 5, 3876-3902.
[21]	Z. Xu, P. Yan, C. Liang, S. Jia, X. Liu, Z. C. Zhang, Chin. J. Catal., 2021, 42, 1586-1592.
[22]	C. N. Neumann, S. J. Rozeveld, M. Dincă, ACS Catal., 2021, 11, 8521-8526.
[23]	K. Sung, M.-H. Lee, Y.-J. Cheong, Y. K. Kim, S. Yu, H.-Y. Jang, Adv. Synth. Catal., 2021, 363, 3090-3097.
[24]	J. Wang, W. Yang, C. Wu, Y. Gong, J. Zhang, C. Shen, ACS Sustainable Chem. Eng., 2020, 8, 16960-16967.
[25]	G. Xu, T. Lammens, Q. Liu, X. Wang, L. Dong, A. Caiazzo, N. Ashraf, J. Guan, X. Mu, Green Chem., 2014, 16, 3971-3977.
[26]	K. Koda, T. Matsu-ura, Y. Obora, Y. Ishii, Chem. Lett., 2009, 38, 838-839.
[27]	O. V. Larina, K. V. Valihura, P. I. Kyriienko, N. V. Vlasenko, D. Y. Balakin, I. Khalakhan, T. Čendak, S. O. Soloviev, S. M. Orlyk, Appl. Catal. A, 2019, 588, 117265.
[28]	A. M. Raspolli Galletti, C. Antonetti, S. Fulignati, D. Licursi, S. Dell’Omo, P. Benito, E. Wilbers, H. J. Heeres, Catal. Today, 2023, 423, 114288.
[29]	R. Palcheva, L. Kaluza, P. Shestakova, J. Moravcik, A. Lyutskanova, K. Soukup, Y. Kalvachev, G. Tyuliev, K. Jiratova, Catal. Today, 2025, 459, 115436.
[30]	X. Han, H. An, X. Zhao, Y. Wang, Catal. Commun., 2020, 146, 106130.
[31]	O. V. Zikrata, O. V. Larina, K. V. Valihura, P. I. Kyriienko, D. Y. Balakin, I. Khalakhan, K. Veltruská, A. Krajnc, G. Mali, S. O. Soloviev, S. M. Orlyk, ACS Sustainable Chem. Eng., 2021, 9, 17289-17300.
[32]	T. Matsu-ura, S. Sakaguchi, Y. Obora, Y. Ishii, J. Org. Chem., 2006, 71, 8306-8308.
[33]	C. Carlini, A. Macinai, A. M. Raspolli Galletti, G. Sbrana, J. Mol. Catal. A, 2004, 212, 65-70.
[34]	G. Li, T. Li, L. Luo, Y. Tan, Z. Lu, Org. Chem. Front., 2025, 12, 4530-4607.
[35]	M. U. Luescher, F. Gallou, B. H. Lipshutz, Chem. Sci., 2024, 15, 9016-9025.
[36]	P. Gandeepan, T. Müller, D. Zell, G. Cera, S. Warratz, L. Ackermann, Chem. Rev., 2019, 119, 2192-2452.
[37]	J. V. Obligacion, P. J. Chirik, Nat. Rev. Chem., 2018, 2, 15-34.
[38]	B. Su, Z.-C. Cao, Z.-J. Shi, Acc. Chem. Res., 2015, 48, 886-896.
[39]	S. Ogoshi, Nickel Catalysis in Organic Synthesis: Methods and Reactions, Wiley-VCH, Weinheim, 2020.
[40]	V. Vermaak, H. C. M. Vosloo, A. J. Swarts, Coord. Chem. Rev., 2024, 507, 215716.
[41]	G. A. Dawson, E. H. Spielvogel, T. Diao, Acc. Chem. Res., 2023, 56, 3640-3653.
[42]	B. C. Lee, C.-F. Liu, L. Q. H. Lin, K. Z. Yap, N. Song, C. H. M. Ko, P. H. Chan, M. J. Koh, Chem. Soc. Rev., 2023, 52, 2946-2991.
[43]	S. Huang, M. Wang, X. Jiang, Chem. Soc. Rev., 2022, 51, 8351-8377.
[44]	X.-Y. Sun, B.-Y. Yao, B. Xuan, L.-J. Xiao, Q.-L. Zhou, Chem Catal., 2022, 2, 3140-3162.
[45]	W. Xue, X. Jia, X. Wang, X. Tao, Z. Yin, H. Gong, Chem. Soc. Rev., 2021, 50, 4162-4184.
[46]	S. Zhu, X. Zhao, H. Li, L. Chu, Chem. Soc. Rev., 2021, 50, 10836-10856.
[47]	A. D. Marchese, T. Adrianov, M. Lautens, Angew. Chem. Int. Ed., 2021, 60, 16750-16762.
[48]	C. Zhu, H. Yue, J. Jia, M. Rueping, Angew. Chem. Int. Ed., 2021, 60, 17810-17831.
[49]	V. P. Ananikov, ACS Catal., 2015, 5, 1964-1971.
[50]	S. Z. Tasker, E. A. Standley, T. F. Jamison, Nature, 2014, 509, 299-309.
[51]	R. Saeb, B. Roh, J. Cornella, Angew. Chem. Int. Ed., 2025, 64, e202424051.
[52]	Z. Huang, M. E. Akana, K. M. Sanders, D. J. Weix, Science, 2024, 385, 1331-1337.
[53]	S. Huang, J. S. Zhou, J. Am. Chem. Soc., 2024, 146, 12895-12900.
[54]	I. Ghosh, N. Shlapakov, T. A. Karl, J. Düker, M. Nikitin, J. V. Burykina, V. P. Ananikov, B. König, Nature, 2023, 619, 87-93.
[55]	M. M. Yamano, A. V. Kelleghan, Q. Shao, M. Giroud, B. J. Simmons, B. Li, S. Chen, K. N. Houk, N. K. Garg, Nature, 2020, 586, 242-247.
[56]	A. García-Domínguez, R. Mondal, C. Nevado, Angew. Chem. Int. Ed., 2019, 58, 12286-12290.
[57]	J. Derosa, R. Kleinmans, V. T. Tran, M. K. Karunananda, S. R. Wisniewski, M. D. Eastgate, K. M. Engle, J. Am. Chem. Soc., 2018, 140, 17878-17883.
[58]	I. Buslov, J. Becouse, S. Mazza, M. Montandon-Clerc, X. Hu, Angew. Chem. Int. Ed., 2015, 54, 14523-14526.
[59]	R. A. Green, J. F. Hartwig, Angew. Chem. Int. Ed., 2015, 54, 3768-3772.
[60]	Z. Zuo, D. T. Ahneman, L. Chu, J. A. Terrett, A. G. Doyle, D. W. C. MacMillan, Science, 2014, 345, 437-440.
[61]	A. K. Bains, A. Biswas, D. Adhikari, Adv. Synth. Catal., 2022, 364, 47-52.
[62]	A. K. Bains, A. Kundu, D. Maiti, D. Adhikari, Chem. Sci., 2021, 12, 14217-14223.
[63]	V. Arora, H. Narjinari, A. Kumar, Organometallics, 2021, 40, 2870-2880.
[64]	R. Babu, M. Subaramanian, S. P. Midya, E. Balaraman, Org. Lett., 2021, 23, 3320-3325.
[65]	Y. Hu, S. Zhang, J. Xu, Y. Liu, A. Yu, J. Qian, Y. Xie, Angew. Chem. Int. Ed., 2023, 62, e202312564.
[66]	Y. Hu, Y. Gu, Y. Dong, Y. Wang, J. Xu, Y. Han, C. Zhang, Y. Xie, Angew. Chem. Int. Ed., 2025, 64, e202502923.
[67]	E. Balaraman, E. Khaskin, G. Leitus, D. Milstein, Nat. Chem., 2013, 5, 122-125.
[68]	R. L. Wingad, P. J. Gates, S. T. G. Street, D. F. Wass, ACS Catal., 2015, 5, 5822-5826.
[69]	N. V. Kulkarni, W. W. Brennessel, W. D. Jones, ACS Catal., 2018, 8, 997-1002.
[70]	S. Fu, Z. Shao, Y. Wang, Q. Liu, J. Am. Chem. Soc., 2017, 139, 11941-11948.
[71]	Y. Xie, Y. Ben-David, L. J. W. Shimon, D. Milstein, J. Am. Chem. Soc., 2016, 138, 9077-9080.
[72]	S. Chakraborty, P. E. Piszel, C. E. Hayes, R. T. Baker, W. D. Jones, J. Am. Chem. Soc., 2015, 137, 14264-14267.
[73]	R. L. Wingad, L. Birch, J. Farndon, J. Lee, K. J. Pellow, D. F. Wass, ChemCatChem, 2023, 15, e202201410.
[74]	G. R. M. Dowson, M. F. Haddow, J. Lee, R. L. Wingad, D. F. Wass, Angew. Chem. Int. Ed., 2013, 52, 9005-9008.
[75]	G.-X. Zhou, C. Hou, Org. Chem. Front., 2024, 12, 115-122.
[76]	Q. Fan, C. Yang, M. Li, G. Wang, X. Kong, Q. Zhu, Dalton Trans., 2025, 54, 1247-1255.
[77]	J. Luo, M. Rauch, L. Avram, Y. Diskin-Posner, G. Shmul, Y. Ben-David, D. Milstein, Nat. Catal., 2020, 3, 887-892.
[78]	S. Mullick, A. Ghosh, D. Banerjee, Chem. Commun., 2024, 60, 4002-4014.
[79]	D. Xu, Y. Wang, M. Ding, X. Hong, G. Liu, S. C. E. Tsang, Chem, 2021, 7, 849-881.
[80]	H. T. Luk, C. Mondelli, D. C. Ferré, J. A. Stewart, J. Pérez-Ramírez, Chem. Soc. Rev., 2017, 46, 1358-1426.
[81]	W. Zhou, Z. Gao, M. Wang, G. Wu, J. Rong, D. Ma, Green Chem., 2022, 24, 5083-5087.
[82]	J. Gu, W. Gong, Q. Zhang, R. Long, J. Ma, X. Wang, J. Li, J. Li, Y. Fan, X. Zheng, S. Qiu, T. Wang, Y. Xiong, Nat. Commun., 2023, 14, 7935.
[83]	Y. Li, W. Gao, M. Peng, J. Zhang, J. Sun, Y. Xu, S. Hong, X. Liu, X. Liu, M. Wei, B. Zhang, D. Ma, Nat. Commun., 2020, 11, 61.

Entry	[Ni]-1 (%)	Base	Conv.^b (%)	Yield^b (%)	TON of Ni ^c
1	[Ni]-1 (0.1 mol%)	NaH	53	47	534
2	[Ni]-1 (0.1 mol%)	^tBuOK	41	41	405
3	[Ni]-1 (0.1 mol%)	^tBuONa	44	44	438
4	[Ni]-1 (0.1 mol%)	CH₃ONa	30	27	302
5	[Ni]-1 (0.1 mol%)	EtONa	48	34	475
6	[Ni]-1 (0.1 mol%)	NaOH	52	44	520
7	[Ni]-1 (0.1 mol%)	K₂CO₃	22	12	224
8	[Ni]-1 (0.1 mol%)	LiH	26	17	258
9 ^d	[Ni]-1 (0.1 mol%)	NaH	61	55	614
10 ^d,e	[Ni]-1 (0.1 mol%)	NaH	72	65	720
11 ^d,e,f	[Ni]-1 (0.1 mol%)	NaH	86	80	855
12 ^f,g,h	[Ni]-1 (0.1 mol%)	NaH	64	54	635
13 ^e,f,i	[Ni]-1 (0.005 mol%)	NaH	71	67	14120
14 ^e,f,i	[Ni]-1 (0.003 mol%)	NaH	62	55	20533
15 ^d,e,f,j	Recovered catalyst	NaH	35	27	345

Entry	[Ni]-1 (%)	Base	Conv.^b (%)	Yield^b (%)	TON of Ni ^c
1	[Ni]-1 (0.1 mol%)	NaH	53	47	534
2	[Ni]-1 (0.1 mol%)	^tBuOK	41	41	405
3	[Ni]-1 (0.1 mol%)	^tBuONa	44	44	438
4	[Ni]-1 (0.1 mol%)	CH₃ONa	30	27	302
5	[Ni]-1 (0.1 mol%)	EtONa	48	34	475
6	[Ni]-1 (0.1 mol%)	NaOH	52	44	520
7	[Ni]-1 (0.1 mol%)	K₂CO₃	22	12	224
8	[Ni]-1 (0.1 mol%)	LiH	26	17	258
9 ^d	[Ni]-1 (0.1 mol%)	NaH	61	55	614
10 ^d,e	[Ni]-1 (0.1 mol%)	NaH	72	65	720
11 ^d,e,f	[Ni]-1 (0.1 mol%)	NaH	86	80	855
12 ^f,g,h	[Ni]-1 (0.1 mol%)	NaH	64	54	635
13 ^e,f,i	[Ni]-1 (0.005 mol%)	NaH	71	67	14120
14 ^e,f,i	[Ni]-1 (0.003 mol%)	NaH	62	55	20533
15 ^d,e,f,j	Recovered catalyst	NaH	35	27	345