Photon-induced regeneration of Pd catalyst for carbonylation of amines to ureas

doi:10.1016/S1872-2067(24)60125-7

Abstract

Abstract:

Substituted ureas hold considerable significance in both natural and synthetic chemicals. Pd-based homogenous catalyst has been used for the urea synthesis, however the aggregation of Pd(0) species leads to the deactivation of the catalyst even under mild conditions. Here, we present a photon-involved carbonylation of amines to synthesize ureas, achieving product yields of up to 99%, using Pd(OAc)₂ and KI without losing the performance owing to the fast regeneration of Pd species under light irradiation. Reaction kinetics results and ultraviolet-visible absorption spectra indicate the regeneration of the Pd species is realized by the light irradiation (below 450 nm) which induces the oxidation reaction between HI and O₂ to produce I₂, so that the active species PdI₂ is regenerated through the reaction between Pd(0) and the I₂.

Key words: Photochemistry, Carbonylation, Pd catalysis, Pd regeneration, Urea

Junbao Peng, Jin Xie, Zelong Li, Can Li. Photon-induced regeneration of Pd catalyst for carbonylation of amines to ureas[J]. Chinese Journal of Catalysis, 2024, 66: 146-151.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60125-7

https://www.cjcatal.com/EN/Y2024/V66/I11/146

Figures/Tables 6

Scheme 1. Various methods of synthesis of urea from amine, R=H or hydrocarbyl.

Table 1 Optimization of reaction condition.

Entry	[Pd] source	[I] source	Solvent	Conversion/ %	Selectivity/ %	Yield^a/ %
1	Pd(OAc)₂	KI	CH₃CN	87	99	86
2	PdCl₂	KI	CH₃CN	88	99	87
3	Pd(acac)₂	KI	CH₃CN	70	96	67
4	Pd(dba)₂	KI	CH₃CN	81	98	79
5^b	Pd(OAc)₂	KI	CH₃CN	58	99	57
6^c	Pd(OAc)₂	KI	CH₃CN	92	99	91
7	—	KI	CH₃CN	Trace	0	0
8	Pd(OAc)₂	—	CH₃CN	Trace	0	0
9^d	Pd(OAc)₂	KI	CH₃CN	Trace	0	0
10^e	Pd(OAc)₂	KI	CH₃CN	Trace	0	0
11^f	Pd(OAc)₂	—	CH₃CN	Trace	0	0
12	Pd(OAc)₂	KI	EtOH	47	94	44
13	Pd(OAc)₂	KI	THF	29	99	29
14	Pd(OAc)₂	KI	Toluene	25	95	24
15	Pd(OAc)₂	TEAI	CH₃CN	39	87	34
16	Pd(OAc)₂	TBAI	CH₃CN	55	99	54
17	Pd(OAc)₂	I₂	CH₃CN	62	98	61
18	Pd(OAc)₂	KBr	CH₃CN	Trace	0	0

Scheme 2. The substrate scope for the synthesis of ureas. Reaction conditions: (A) Symmetrical ureas. 1 (1.0 mmol), CO/O2 (balloon), CH3CN (8 mL), 20W blue LED, isolated yields. a 48 h. b Ethylene glycol dimethyl ether (DME) as solvent. (B) Unsymmetrical ureas. 1 (0.5 mmol), 1’ (1.0 mmol), CO/O2 (balloon), CH3CN (8 mL), 20 W blue LED, isolated yields. a 72 h.

Fig. 1. Investigation of the reaction mechanism. (A) Using I2 to replace KI and under dark. 1a (1.0 mmol), CO (balloon), CH3CN (8 mL), GC yield based on I2, n-hexadecane as internal standard. (B) Add 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). 1a (1.0 mmol), CO/O2 (balloon), CH3CN (8 mL), 20 W blue LED, GC yield, n-hexadecane as internal standard. (C,D) UV-visible absorption spectrum. (E) Effect of different wavelengths on activity. 1a (1.0 mmol), CO/O2 (balloon), CH3CN (8 mL), Xe lamp with or without filter, GC yield, n-hexadecane as internal standard.

Scheme 3. Possible mechanism of the reaction (other ligands were omitted).

Scheme 4. Gram-scale reaction and synthesis of antifilarial drug. Reaction conditions: (A) Gram-scale reaction of morpholine. 1a (5.0 mmol), CO/O2 (balloon), CH3CN (20 mL), 20 W blue LED, isolated yields, (B) Synthesis of antifilarial drug. 1l (0.5 mmol), 1m (1mmol), CO/O2 (balloon), DME (8 mL), 20 W blue LED, isolated yields, a 1l (5 mmol), 1m (10 mmol), DME (20 mL), 72 h, GC yield.

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