A stable acyl cobalt-based catalyst with exceptionally elevated activity for the carbonylation of epoxides into β-lactones

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60182-8

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

Figures/Tables 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.

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