Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO2

doi:10.1016/S1872-2067(21)63848-2

Abstract

Abstract:

The role of carbodiimide as dehydrant in the chemo-, regio- and stereoselective Pd (II/0)-catalyzed hydrocarboxylation of various alkynes with HCOOH releasing CO in situ is reported for the first time to obtain α,β-unsaturated carboxylic acids. Both symmetrical and unsymmetrical monoalkynes show good reactivity. Importantly, 2,2’-(1,4-phenylene)diacrylic acid can also be synthesized in high yield through the dihydrocarboxylation of 1,4-diethynylbenzene. Besides, an excellent result in gram scale experiment and TON up to 900 can be obtained, displaying the efficiency of this protocol. Notably, regulating the types and concentrations of dehydrant can control the CO generation, avoiding directly operating toxic CO and circumventing sensitivity issue to the CO amount. On the basis of the attractive features of formic acid including easy preparation through CO₂ hydrogenation and efficient liberation of CO, this protocol using formic acid as bridging reagent between CO₂ and CO can be perceived as an indirect utilization of CO₂, offering an alternative method for preparing acrylic acid analogues.

Key words: Carbodiimide, Hydrocarboxylation, Formic acid, CO₂ indirect utilization, α,β-Unsaturated carboxylic acids, Synthetic method

Shu-Mei Xia, Zhi-Wen Yang, Kai-Hong Chen, Ning Wang, Liang-Nian He. Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO₂[J]. Chinese Journal of Catalysis, 2022, 43(7): 1642-1651.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63848-2

https://www.cjcatal.com/EN/Y2022/V43/I7/1642

Figures/Tables 12

Fig. 1. Transition-metal-catalyzed hydrocarboxylation of alkynes with C1 sources.

Fig. 2. Optimization of the reaction conditions. (a) Effect of 1 mol% different catalysts. (b) Effect of 2 mol% different ligands. (c) Effect of 20 mol% different dehydrants. Template reaction conditions: 1a (1 mmol), Pd(OAc)2 (1 mol%), Xantphos (2 mol%), HCOOH (1.5 mmol), DCC (20 mol%), toluene (2 mL), 80 °C, 12 h, Ar atmosphere. Yields were determined by 1H NMR with triphenylmethane as internal standard. a Ligand (4 mol%). b Ligand (1 mol%). c Pd(OAc)2 (0.2 mol%), Xantphos (0.4 mol%). d Pd(PPh3)4 (0.1 mol%), Xantphos (0.2 mol%).

Fig. 3. The effect of the amount of DCC on the hydrocarboxylation reaction. Reaction conditions: 1a (1 mmol), Pd(OAc)2 (0.2 mol%), Xantphos (0.4 mol%), HCOOH (1.5 mmol), DCC (x mol% relative to 1a), toluene (2 mL), 80 °C, 12 h.

Scheme 1. Scope of symmetric alkynes. Standard conditions: symmetric alkyne 1 (1.0 mmol), Pd(OAc)2 (0.2 mol%), Xantphos (0.4 mol%), HCOOH (1.5 mmol), DCC (20 mol%), toluene (2 mL), 80 °C, 12 h, Ar atmosphere. The yield was determined by 1H NMR with triphenylmethane as internal standard, isolated yields were shown in brackets. a 1a (10.0 mmol), 20 h or 48 h. b Pd(OAc)2 (0.02 mol%), Xantphos (0.04 mol%). c Pd(OAc)2 (0.4 mol%), Xantphos (0.8 mol%).

Scheme 2. Scope of unsymmetric alkynes. The reactions were carried out with internal alkyne (1.0 mmol), Pd(OAc)2 (0.4 mol%), Xantphos (0.8 mol%), HCOOH (1.5 mmol), DCC (20 mol%), toluene (2 mL), 80 °C, 12 h, Ar atmosphere. The yield and the ratio of α and β were determined by 1H NMR with triphenylmethane as internal standard, isolated yield was shown in brackets. a Pd(OAc)2 (1 mol%), Xantphos (2 mol%), 20 h. b α and β configuration couldn’t be distinguished from 1H NMR spectra.

Scheme 3. Scope of terminal alkynes. All reactions were performed in toluene (2 mL) at 80 °C for 20 h in the presence of terminal alkyne (1 mmol), Pd(OAc)2 (1 mol%), Xantphos (2 mol%), HCOOH (1.5 mmol), DCC (20 mol%). The yield and the ratio of α and β were determined by 1H NMR with triphenylmethane as internal standard, isolated yields were shown in brackets. a HCOOH (3 mmol), DCC (40 mol%).

Scheme 4. 13C-Labeling and D-labeling experiments. The yield was determined by 1H NMR with triphenylmethane as internal standard.

Scheme 5. Hydrocarboxylation of 1,2-diphenylethyne with labeled compounds. The yield was determined by 1H NMR with triphenylmethane as internal standard; isolated yields are in brackets.

Table 1 Control experiments: the role of HCOOH.a


Entry	HCOOH/x mmol	DCC/y mol%	CO/z	2a Yield ^b/%
1	0	20	1 atm	—
2	0	20	200 μmol	—
3	1.5	—	200 μmol	64
4	1.5	20	—	97

Fig. 4. The relationship between the release amount of CO from dehydrant and the reaction outcome. Reaction conditions A: diphenylacetylene 1a (1 mmol), Pd(OAc)2 (0.2 mol%), Xantphos (0.4 mol%), dehydrant (20 mol%), HCOOH (1.5 mmol), toluene (2 mL), 80 °C, 12 h, yield determined by 1H NMR. Reaction conditions B: Pd(OAc)2 (0.2 mol%), Xantphos (0.4 mol%), HCOOH (1.5 mmol), dehydrant (20 mol%), toluene (2 mL), 80 °C, 12 h, Ar atmosphere, the release amount of CO was determined by GC with CH4 as internal standard. a No dehydrant. b No dehydrant, CO (200 μmol).

Scheme 6. DFT calculations on catalyst poisoning for (Xantphos)Pd(CO).

Fig. 5. Proposed mechanism for the Pd-catalyzed regioselective hydrocarboxylation using HCOOH.

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Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO₂

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