Solvent-scissors overcoming inert hydrogen bonding enable efficient oxidation of aromatic hydrocarbons under atmospheric oxygen

doi:10.1016/S1872-2067(24)60042-2

Abstract

Abstract:

Hydrogen bonding is a fascinating interaction that controls the outcomes of chemical reactions. However, overcoming the strong deactivation arising from alterations in the polarity and electronic properties of the reactants and intermediates remains a challenge. Herein, we proposed a “solvent-scissors” strategy for overcoming the inert hydrogen bonding, enabling the efficient aerobic oxidation of methyl aromatics into aromatic acids under atmospheric oxygen at 25‒45 °C. The hydrogen bonds between the key intermediate, benzaldehyde (PhCHO), and hexafluoroisopropanol (HFIP) were reconstructed using solvent-scissors (acetic acid (HOAc), ethyl acetate, ethyl chloroacetate, and methyl chloroacetate), which promoted the release of free PhCHO from its inert hydrogen-bonded state and enabled the one-step oxidation of toluene to benzoic acid under mild conditions. The standard Gibbs free energy changes (ΔG⁰) representing the proton acceptance capability of the solvent were of the same order of magnitude as the turnover number (TON) (capacity for promoting benzaldehyde oxidation). This approach affords remarkable benzoic acid selectivity (98.7%) with high toluene conversion (96.8%) at 45 °C within 4 h under 0.1 MPa O₂ using NHPI/metal acetate/HFIP-HOAc. This strategy opens up a new avenue for regulating hydrogen bonding in a wider range of applications for the planning and development of synthesis protocols.

Key words: Hydrogen bonding, Aromatic hydrocarbon, Selective Oxidation, Solvent-scissors, Hexafluoroisopropanol

Kui Jin, Meiyun Zhang, Penghua Che, Dongru Sun, Yong Wang, Hong Ma, Qiaohong Zhang, Chen Chen, Jie Xu. Solvent-scissors overcoming inert hydrogen bonding enable efficient oxidation of aromatic hydrocarbons under atmospheric oxygen[J]. Chinese Journal of Catalysis, 2024, 61: 322-330.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60042-2

https://www.cjcatal.com/EN/Y2024/V61/I6/322

Figures/Tables 8

Scheme 1. Mechanism of stabilizing and releasing PhCHO by modulating hydrogen bonding.

Fig. 1. Red bars represent molePhCOOH/(molePhCHO + molePhCOOH) ratio; blue bars represent molePhCHO/(molePhCHO + molePhCOOH) ratio. (a) Toluene (0.5 mmol), NHPI (0.05mmol), Co(OAc)2·4H2O (0.01 mmol), O2 (0.1 MPa), HFIP:X = 1:1, 45 °C, 4 h. (b) PhCHO (0.5 mmol), NHPI (0.05 mmol), Co(OAc)2·4H2O (0.01 mmol), O2 (0.1 MPa), HFIP:X = 1:1, 25 °C, 1 h.

Table 1 Comparison of effect of solvent on toluene oxidation under the optimized conditions.

Entry	Solvent	Conv. (mol%)	Yield (mol%)
Entry	Solvent	Conv. (mol%)	PhCHO	PhCOOH
1	HFIP	96.4	63.7	29.1
2	HOAc	71.8	1.8	69.9
3	HFIP-HOAc	96.8	1.4	95.5

Fig. 2. (a) Concentration-dependence of 1H-NMR spectra of HFIP-X1 (acetic acid). (b) HFIP-X5 (dichloromethane). (c) HFIP-X2 (ethyl acetate); (d) HFIP-X3 (ethyl chloroacetate). (e) HFIP-X4 (methyl chloroacetate), respectively (700 MHz, CDCl3).

Fig. 3. (a) Plots of 1/C versus 1/Δδ with HFIP as donor and X as acceptor. (b) The time profile of PhCHO oxidation at room temperature using the NHPI/Co(OAc)2 catalytic system. Reaction conditions: PhCHO (0.5 mmol), NHPI (0.05 mmol), Co(OAc)2·4 H2O (0.01 mmol), O2 (0.1 MPa), 25 °C, HFIP + X = 1 ml, HFIP:X = 4:1. (c) TON values for PhCHO oxidation in different scissor solvents X and ?ΔG0 of HFIP-X.

Table 2 Parameters of hydrogen bonds determined by 1H-NMR.

X	A	b	K_HB (L/mol)	ΔG⁰ (kJ/mol)
PhCHO	0.0830	0.2526	3.041	−2.757
X1	0.0190	0.1085	5.711	−4.319
X2	0.0629	0.2505	3.984	−3.426
X3	0.1487	0.3335	2.243	−2.002
X4	0.1740	0.3340	1.9190	−1.616

Fig. 4. (a) In-situ FT-IR spectra of PhCHO with the sequential addition of HFIP and X3; red ?: 0.5 mL of HFIP was added; blue ?: 0.5 mL of X3 was added. (b) FT-IR spectra of A (PhCHO), B (PhCHO: HFIP = 1:2), and C (PhCHO:HFIP:X3 = 1:2:2.5). (c,d) Fitting results in C=O region after sequential addition of HFIP and X3 to PhCHO. The red dotted line indicates fitting results. Free PhCHO (Free-A) and hydrogen-bonded PhCHO (HB-A) are respectively represented by the red (1704 cm?1) and blue regions (1693 cm?1).

Table 3 Catalytic oxidation of various methyl aromatics to aromatic acids using NHPI/Co2+/HFIP/X1.

Time (h)	HFIP:X1 ratio	Conv. (mol%)	Select. (mol%)
4	4:6	98	96
8	3:7	94	90
4	4:6	98	90
8	4:6	94	93
8	4:6	61	84
8	4:6	98	54

References

[1]	J. N. H. Reek, B. de Bruin, S. Pullen, T. J. Mooibroek, A. M. Kluwer, X. Caumes, Chem. Rev., 2022, 122, 12308-12369.
[2]	D. T. J. Morris, S. M. Wales, D. P. Tilly, E. H. E. Farrar, M. N. Grayson, J. W. Ward, J. Clayden, Chem, 2021, 7, 2460-2472.
[3]	A. L. Thompson, N. G. White, Chem. Soc. Rev., 2023, 52, 6254-6269.
[4]	Y. J. Guo, S. J. Li, Y. L. Sun, L. Wang, W. M. Zhang, P. Zhang, Y. Lan, Y. Li, Green Chem., 2021, 23, 7041-7052.
[5]	V. Dantignana, M. Milan, O. Cusso, A. Company, M. Bietti, M. Costas, ACS Cent. Sci., 2017, 3, 1350-1358.
[6]	M. Borrell, S. Gil-Caballero, M. Bietti, M. Costas, ACS Catal., 2020, 10, 4702-4709.
[7]	H. Wang, Y. F. Zhao, F. T. Zhang, Z. G. Ke, B. X. Han, J. F. Xiang, Z. P. Wang, Z. M. Liu, Sci. Adv., 2021, 7, eabg0396.
[8]	Z. Zhu, C. M. Glinkerman, D. L. Boger, J. Am. Chem. Soc., 2020, 142, 20778-20787.
[9]	Y. Shang, S. Chen, N. Chen, Y. Li, J. Lai, Y. Ma, J. Chen, F. Wu, R. Chen, Energy Environ. Sci., 2022, 15, 2653-2663.
[10]	H. V. D. Nguyen, R. De Vries, S. D. Stoyanov, ACS Sustainable Chem. Eng., 2020, 8, 14166-14178.
[11]	S. Hu, D. Jiang, L. Gu, G. Xu, Z. Li, Y. Yuan, Chem. Eng. J., 2020, 399, 125847.
[12]	M. J. Chen, T. Runge, L. L. Wang, R. M. Li, J. Feng, X. L. Shu, Q. S. Shi, Carbohydr. Polym., 2018, 200, 115-121.
[13]	W. Q. Li, C. Molina-Fernández, J. Estager, J. C. M. Monbaliu, D. P. Debecker, P. Luis, J. Membr. Sci., 2020, 598, 117790.
[14]	Y. Xu, P. M. J. Szell, V. Kumar, D. L. Bryce, Coord. Chem. Rev., 2020, 411, 213237.
[15]	V. A. Lorenz-Fonfria, Chem. Rev., 2020, 120, 3466-3576.
[16]	X. Yi, W. Chen, Y. Xiao, F. Liu, X. Yu, A. Zheng, J. Am. Chem. Soc., 2023, 145, 27471-27479.
[17]	Y. Yang, J. Lan, J. You, Chem. Rev., 2017, 117, 8787-8863.
[18]	C. Chen, X. Pang, Y. Li, X. Yu, Small, 2023, 2305875.
[19]	M. Huda, K. Minamisawa, T. Tsukamoto, M. Tanabe, K. Yamamoto, Angew. Chem. Int. Ed., 2019, 58, 1002-1006.
[20]	X. Tang, X. Jia, Z. Huang, Chem. Sci., 2018, 9, 288-299.
[21]	Y. Wang, P. Hu, J. Yang, Y. A. Zhu, D. Chen, Chem. Soc. Rev., 2021, 50, 4299-4358.
[22]	J. Helberg, D. A. Pratt, Chem. Soc. Rev., 2021, 50, 7343-7358.
[23]	S. H. Kyne, G. Lefevre, C. Ollivier, M. Petit, V. A. Ramis Cladera, L. Fensterbank, Chem. Soc. Rev., 2020, 49, 8501-8542.
[24]	H. F. Motiwala, A. M. Armaly, J. G. Cacioppo, T. C. Coombs, K. R. K. Koehn, V. M. t. Norwood, J. Aube, Chem. Rev., 2022, 122, 12544-12747.
[25]	I. Colomer, A. E. R. Chamberlain, M. B. Haughey, T. J. Donohoe, Nat. Rev. Chem., 2017, 1, 0088.
[26]	H. F. Motiwala, M. Charaschanya, V. W. Day, J. Aube, J. Org. Chem., 2016, 81, 1593-1609.
[27]	S. Zhang, M. Vayer, F. Noël, V. D. Vuković, A. Golushko, N. Rezajooei, C. N. Rowley, D. Lebœuf, J. Moran, Chem, 2021, 7, 3425-3441.
[28]	Y. Yoshino, Y. Hayashi, T. Iwahama, S. Sakaguchi, Y. Ishii, J. Org. Chem., 1997, 62, 6810-6813.
[29]	E. Gaster, S. Kozuch, D. Pappo, Angew. Chem. Int. Ed., 2017, 56, 5912-5915.
[30]	S. Li, L. Cai, H. Ji, L. Yang, G. Li, Nat. Commun., 2016, 7, 10443.
[31]	J. D. Piper, P. W. Piper, Compr. Rev. Food Sci. Food Saf., 2017, 16, 868-880.
[32]	A. K. Suresh, M. M. Sharma, T. Sridhar, Ind. Eng. Chem. Res., 2000, 39, 3958-3997.
[33]	Y. Luo, H. Ma, S. Zhang, D. Zheng, P. Che, X. Liu, M. Zhang, J. Gao, J. Xu, J. Am. Chem. Soc., 2020, 142, 6085-6092.
[34]	X. Liu, Y. Luo, H. Ma, S. Zhang, P. Che, M. Zhang, J. Gao, J. Xu, Angew. Chem. Int. Ed., 2021, 60, 18103-18110.
[35]	J. J. B. van der Tol, G. Vantomme, E. W. Meijer, J. Am. Chem. Soc., 2023, 145, 17987-17994.
[36]	J. Zhong, M. A. Carignano, S. Kais, X. C. Zeng, J. S. Francisco, I. Gladich, J. Am. Chem. Soc., 2018, 140, 5535-5543.
[37]	S. Xu, G. Shi, Y. Feng, C. Chen, L. Ji, Mol. Catal., 2020, 498, 111244.
[38]	Y. Ishii, T. Iwahama, S. Sakaguchi, K. Nakayama, Y. Nishiyama, J. Org. Chem., 1996, 61, 4520-4526.
[39]	A. Yokozeki, D. J. Kasprzak, M. B. Shiflett, Appl. Energy, 2007, 84, 863-873.
[40]	S. Civis, M. Lamanec, V. Spirko, J. Kubista, M. Spet'ko, P. Hobza, J. Am. Chem. Soc., 2023, 145, 8550-8559.
[41]	S. D. Fried, S. Bagchi, S. G. Boxer, J. Am. Chem. Soc., 2013, 135, 11181-11192.
[42]	G. F. Li, S. Ye, S. Morita, T. Nishida, M. Osawa, J. Am. Chem. Soc., 2004, 126, 12198-12199.
[43]	K. I. Oh, K. Rajesh, J. F. Stanton, C. R. Baiz, Angew. Chem. Int. Ed., 2017, 56, 11375-11379.
[44]	H. Sterckx, B. Morel, B. U. W. Maes, Angew. Chem. Int. Ed., 2019, 58, 7946-7970.