酰基钴基催化剂用于高活性高稳定性环氧化物羰基化制备β-内酯

doi:10.1016/S1872-2067(24)60182-8

摘要/Abstract

摘要：

聚羟基烷酸酯(PHA)是一种被广泛应用的可生物降解聚合物, 其单体为β-内酯, 可以通过使用结构明确的[Lewis酸]+[Co(CO)₄]^‒催化剂对环氧化物进行扩环羰基化选择性合成. 然而, 当温度高于80 °C时, [Co(CO)₄]^‒物种易分解, 因而制约了在高温反应条件下商业可行的工艺的发展. HCo(CO)₄催化的氢甲酰化过程中涉及稳定的{(acyl)Co(CO)_n}中间体, 因此我们致力于提升高温条件下催化剂催化环氧化开环羰基化活性. 本文制备的[(acetyl)Co(CO)₂dppp]和[(TPP)CrCl]催化剂体系表现出较好的催化性能, 100 °C时初始转化频率达到4700 h^‒1, 转化数为93000. 而且该催化剂还表现出较好的稳定性, 在80 °C运行168 h, 仍能选择性地产生β-内酯

关键词: 环氧化物羰基化, β-内酯, 四羰基钴, 酰基羰基钴, 高温催化活性

Abstract:

Polyhydroxyalkanoate (PHA), a well-known biodegradable polymer, features β-lactones as its monomers, which can be selectively synthesized through ring-expansion carbonylation of epoxides using well-defined [Lewis acid]⁺[Co(CO)₄]^- catalysts. However, the decomposition of [Co(CO)₄]^- species at temperatures exceeding 80 °C presents a hurdle for the development of commercially viable processes under high-temperature reaction conditions to reduce reaction time. Drawing insights from stable {(acyl)Co(CO)_n} intermediates involved in historical HCo(CO)₄-catalyzed hydroformylation processes, we sought to the high-temperature catalytic activity of epoxide ring-expansion carbonylation. The developed catalyst system, [(acetyl)Co(CO)₂dppp] and [(TPP)CrCl], exhibited exceptional catalytic performance with an unprecedented initial turnover frequency of 4700 h^-1 at 100 °C and a turnover numbers of 93000. Notably, the catalyst displayed outstanding stability, operating at 80 °C for 168 h while selectively generating β-lactones.

Key words: Epoxide carbonylation, β-Lactone, Cobalt tetracarbonyl, Acyl cobalt carbonyl, High-temperature catalytic activity

姜建伟, Vinothkumar Ganesan, 崔仁洛, 申庭澈, 尹城镐, 朴纪映. 酰基钴基催化剂用于高活性高稳定性环氧化物羰基化制备β-内酯[J]. 催化学报, 2025, 68: 336-344.

Jianwei Jiang, Vinothkumar Ganesan, Inrack Choi, Jeongcheol Shin, Sungho Yoon, Kiyoung Park. A stable acyl cobalt-based catalyst with exceptionally elevated activity for the carbonylation of epoxides into β-lactones[J]. Chinese Journal of Catalysis, 2025, 68: 336-344.

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https://www.cjcatal.com/CN/Y2025/V68/I1/336

图/表 8

Scheme 1. A schematic representation depicting the synthesis of diverse compounds from epoxides via ring expansion carbonylation.

Table 1 The results of the HO carbonylation reaction under various reaction conditions using the [(acetyl)Co(CO)2dppp]/[(TPP)CrCl] catalyst system.

Entry	Cat.	HO/ Co^a	T (°C)	Time (h)	CO (bar)	Conv.^b (%)	Selectivity^c (%) lac., ket., ald., iso., hex.	β-lactone yield^d (%)	β-lactone TON^e
1	2	10000	80	24	60	>97	> 96, < 1, < 1, < 1, < 1	93	9,300
2	1	10000	80	24	60	>97	> 96, < 1, < 1, < 1, < 1	93	9,300
3	2	10000	80	24	30	25	> 96, < 1, < 1, < 1, < 1	24	2,400
4	2	10000	80	24	10	0
5	2	10000	60	24	60	0
6	2	100000	80	168	60	>97	> 96, < 1, < 1, < 1, < 1	93	93,000

Fig. 1. 1H NMR spectra of (a) crude product mixture from HO carbonylation and (b) starting material HO.

Fig. 2. Comparative analysis of the TON based on reaction time between [(TPP)Cr(THF)2]+[Co(CO)4]- (○) and catalyst system 2 (■) at a reaction temperature of 80 °C, with a HO/catalyst ratio of 50000.

Fig. 3. 1H NMR spectra of [(acetyl)Co(CO)2dppp] (a), the mixture before reaction having [(acetyl)Co(CO)2dppp]/[(TPP)CrCl] (b), the product generating after carbonylation (HO:Co:Cr = 10:1:1, 80 °C, 10 h, DME solvent, 60 bar CO) (c).

Fig. 4. DFT-calculated reaction profiles for the PO carbonylation reaction catalyzed by (a) [(acetyl)Co(CO)2(dmpp)] and (b) [Co(CO)4]- catalysts. The free energies are given in kcal/mol and the energy barriers of individual steps are given in parentheses.

Fig. 5. DFT-computed LUMOs of four-coordinate [(acetyl)Co(CO)2L(dmpp)] species containing η2-type interaction with the acyl carbonyl group (a) and agostic interaction with the acyl C-H bond (b).

Scheme 2. Proposed mechanism for [(acetyl)Co(CO)2dppp]/[(TPP)CrCl] catalyzed epoxide carbonylation.

参考文献

[1]	Y. D. Y. L. Getzler, V. Mahadevan, E. B. Lobkovsky, G. W. Coates, J. Am. Chem. Soc., 2002, 124, 1174-1175.
[2]	V. Mahadevan, Y. D. Y. L. Getzler, G. W. Coates, Angew. Chem. Int. Ed., 2002, 41, 2781-2784.
[3]	J. A. R. Schmidt, V. Mahadevan, Y. D. Y. L. Getzler, G. W. Coates, Org. Lett., 2004, 6, 373-376.
[4]	J. A. R. Schmidt, E. B. Lobkovsky, G. W. Coates, J. Am. Chem. Soc., 2005, 127, 11426-11435.
[5]	J. W. Kramer, E. B. Lobkovsky, G. W. Coates, Org. Lett., 2006, 8, 3709-3712.
[6]	T. L. Church, Y. D. Y. L. Getzler, G. W. Coates, J. Am. Chem. Soc., 2006, 128, 10125-10133.
[7]	J. M. Rowley, E. B. Lobkovsky, G. W. Coates, J. Am. Chem. Soc., 2007, 129, 4948-4960.
[8]	J. W. Kramer, D. Y. Joh, G. W. Coates, Org. Lett., 2007, 9, 5581-5583.
[9]	T. L. Church, Y. D. Y. L. Getzler, C. M. Byrne, G. W. Coates, Chem. Commun., 2007, 657-674.
[10]	M. Mulzer, B. T. Whiting, G. W. Coates, J. Am. Chem. Soc., 2013, 135, 10930-10933.
[11]	M. Mulzer, G. W. Coates, J. Org. Chem., 2014, 79, 11851-11862.
[12]	M. Mulzer, J. R. Lamb, Z. Nelson, G. W. Coates, Chem. Commun., 2014, 50, 9842-9845.
[13]	J. W. Kramer, J. M. Rowley, G. W. Coates, Ring-expanding carbonylation of epoxides. In Organic Reactions, John Wiley and Sons, Inc., New York: Chapman and Hall, Ltd., London, 2004.
[14]	E. W. Dunn, J. R. Lamb, A. M. LaPointe, G. W. Coates, ACS Catal., 2016, 6, 8219-8223.
[15]	A. K. Hubbell, A. M. LaPointe, J. R. Lamb, G. W. Coates, J. Am. Chem. Soc., 2019, 141, 2474-2480.
[16]	J. R. Lamb, A. K. Hubbell, S. N. MacMillan, G. W. Coates, J. Am. Chem. Soc., 2020, 142, 8029-8035.
[17]	A. K. Hubbell, J. R. Lamb, K. Klimovica, M. Mulzer, T. D. Shaffer, S. N. MacMillan, G. W. Coates, ACS Catal., 2020, 10, 12537-12543.
[18]	A. K. Hubbell, G. W. Coates, J. Org. Chem., 2020, 85, 13391-13414.
[19]	M. Allmendinger, R. Eberhardt, G. Luinstra, B. Rieger, J. Am. Chem. Soc., 2002, 124, 5646-5647.
[20]	F. Molnar, G. A. Luinstra, M. Allmendinger, B. Rieger, Chem. - Eur. J., 2003, 9, 1273-1280.
[21]	M. Allmendinger, M. Zintl, R. Eberhardt, G. A. Luinstra, F. Molnar, B. Rieger, J. Organomet. Chem., 2004, 689, 971-979.
[22]	M. Allmendinger, F. Molnar, M. Zintl, G. A. Luinstra, P. Preishuber-Pflügl, B. Rieger, Chem.-Eur. J., 2005, 11, 5327-5332.
[23]	K. Khumtaveeporn, H. Alper, Acc. Chem. Res., 1995, 28, 414-422.
[24]	K. Okuro, D. Tuan, K. Khumtaveeporn, H. Alper, Tetrahedron Lett., 1996, 37, 2713-2716.
[25]	J. T. Lee, P. J. Thomas, H. Alper, J. Org. Chem., 2001, 66, 5424-5426.
[26]	J. T. Lee, H. Alper, Macromolecules, 2004, 37, 2417-2421.
[27]	J. M. Pollock, A. J. Shipman, GB 1020575 A, 1966.
[28]	Y. Kamiya, K. Kawato, H. Ohta, Chem. Lett., 1980, 9, 1549-1552.
[29]	K. Nakano, K. Fumitaka, K. Nozaki, J. Polym. Sci., Part A: Polym. Chem., 2004, 42, 4666-4670.
[30]	K. Nakano, K. Nozaki, Carbonylation of Epoxides. Topics in Organometallic Chemistry, vol 18, Springer, Berlin, Heidelberg, 2006.
[31]	E. Drent, E. Kragtwijk, EP 577206 A2, 1994.
[32]	A. Stirling, M. Iannuzzi, M. Parrinello, F. Molnar, V. Bernhart, G. A. Luinstra, Organometallics, 2005, 24, 2533-2537.
[33]	C. Y. Huang, A. G. Doyle, Chem. Rev., 2014, 114, 8153-8198.
[34]	P. Ganji, D. J. Doyle, H. Ibrahim, Org. Lett., 2011, 13, 3142-3145.
[35]	P. Ganji, H. Ibrahim, Chem. Commun., 2012, 48, 10138-10140.
[36]	Y. Zhang, J. Ji, X. Zhang, S. Lin, Q. Pan, L. Jia, Org. Lett., 2014, 16, 2130-2133.
[37]	H. D. Park, M. Dincă, Y. Román-Leshkov, ACS Cent. Sci., 2017, 3, 444-448.
[38]	E. R. Baral, D. Kim, S. Lee, M. H. Park, J. G. Kim, Catalysts, 2019, 9, 311.
[39]	L. He, J. C. Yang, T. T. Song, Y. Liu, X. B. Lu, Eur. J. Inorg. Chem., 2022, 2022, e202200496.
[40]	J. C. Yang, J. Yang, W. B. Li, X. B. Lu, Y. Liu, Angew. Chem. Int. Ed., 2022, 61, e202116208.
[41]	H. Li, Y. Tang, Z. Li, Y. Li, B. Chen, C. Shen, Z. Huang, K. Dong, Mol. Catal., 2022, 533, 112779.
[42]	L. Jens, L. Matthias, G. Christoph, R. Suresh, US Patent, 0204465 A1, 2022.
[43]	J. B. Peng, F. P. Wu, X. F. Wu, Chem. Rev., 2019, 119, 2090-2127.
[44]	S. Rajendiran, P. Natarajan, S. Yoon, RSC Adv., 2017, 7, 4635-4638.
[45]	S. Rajendiran, V. Ganesan, S. Yoon, Inorg. Chem., 2019, 58, 3283-3289.
[46]	V. Ganesan, S. Yoon, ACS Appl. Mater. Interfaces, 2019, 11, 18609-18616.
[47]	V. Ganesan, S. Yoon, Inorg. Chem., 2020, 59, 2881-2889.
[48]	V. Ganesan, S. Yoon, Catalysts, 2020, 10, 905.
[49]	V. Ganesan, S. Yoon, Chin. J. Chem., 2023, 41, 3560-3566.
[50]	V. Ganesan, S. Yoon, Bull. Korean Chem. Soc., 2023, 44, 1049-1055.
[51]	J. Jiang, S. Rajendiran, L. Piao, S. Yoon, Top. Catal., 2017, 60, 750-754.
[52]	J. Jiang, S. Yoon, Sci. Rep., 2018, 8, 13243.
[53]	J. Jiang, S. Rajendiran, S. Yoon, Asian J. Org. Chem., 2019, 8, 151-154.
[54]	J. Jiang, S. Yoon, J. Mater. Chem. A, 2019, 7, 6120-6125.
[55]	S. Yoon, S. Rajendiran, J. Jiang, K. Park, US Patent 11648545 B2, 2023.
[56]	M. Zintl, F. Molnar, T. Urban, V. Bernhart, P. Preishuber-Pflügl, B. Rieger, Angew. Chem. Int. Ed., 2008, 47, 3458-3460.
[57]	E. W. Dunn, G. W. Coates, J. Am. Chem. Soc., 2010, 132, 11412-11413.
[58]	T. Ebrahimi, D. C. Aluthge, S. G. Hatzikiriakos, P. Mehrkhodavandi, Macromolecules, 2016, 49, 8812-8824.
[59]	M. Suzuki, Y. Tachibana, K. I. Kasuya, Polym. J., 2021, 53, 47-66.
[60]	U. Herrmann, G. Emig, Ind. Eng. Chem. Res., 1998, 37, 759-769.
[61]	A. Corma, S. Iborra, A. Velty, Chem. Rev., 2007, 107, 2411-2502.
[62]	X. Di, C. Li, B. Zhang, J. Qi, W. Li, D. Su, C. Liang, Ind. Eng. Chem. Res., 2017, 56, 4672-4683.
[63]	R. F. Heck, J. Am. Chem. Soc., 1963, 85, 1460-1463.
[64]	F. Hebrard, P. Kalck, Chem. Rev., 2009, 109, 4272-4282.
[65]	J. M. Birbeck, A. Haynes, H. Adams, L. Damoense, S. Otto, ACS Catal., 2012, 2, 2512-2523.
[66]	D. M. Hood, R. A. Johnsond, A. E. Carpenter, J. M. Younker, D. J. Vinyard, G. G. Stanley, Science, 2020, 367, 542-548.
[67]	B. Zhang, C. Kubis, R. Franke, Science, 2022, 377, 1223-1227.
[68]	M. Solà, T. Ziegler, Organometallics, 1996, 15, 2611-2618.
[69]	S. K. Goh, D. S. Marynick, Organometallics, 2002, 21, 2262-2267.
[70]	C. F. Huo, Y. W. Li, M. Beller, H. Jiao, Organometallics, 2003, 22, 4665-4677.
[71]	S. Maeda, K. Morokuma, J. Chem. Theory Comput., 2012, 8, 380-385.
[72]	R. F. Heck, D. S. Breslow, J. Am. Chem. Soc., 1962, 84, 2499-2502.
[73]	Y. Permana, K. Nakano, M. Yamashita, D. Watanabe, K. Nozaki, Chem. Asian J., 2008, 3, 710-718.