光子诱导Pd催化剂的再生用于胺羰基化合成脲

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

催化学报 ›› 2024, Vol. 66: 146-151.DOI: 10.1016/S1872-2067(24)60125-7

光子诱导Pd催化剂的再生用于胺羰基化合成脲

彭俊保^a, 解进^a, 李泽龙^a^,^*(), 李灿^a^,^b^,^*()

^a兰州大学化学化工学院, 甘肃省先进催化重点实验室, 功能有机化学国家重点实验室, 甘肃兰州 730000
^b中国科学院大连化学物理研究所, 催化基础国家重点实验室, 大连洁净能源国家实验室, 辽宁大连 116023

收稿日期:2024-07-18 接受日期:2024-08-26 出版日期:2024-11-18 发布日期:2024-11-10
通讯作者: *电子信箱: Lizl@lzu.edu.cn (李泽龙),canli@dicp.ac.cn (李灿).
基金资助:
国家自然科学基金(22072061);国家重点研发计划(2021YFA15011)

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

Junbao Peng^a, Jin Xie^a, Zelong Li^a^,^*(), Can Li^a^,^b^,^*()

^aKey Laboratory of Advanced Catalysis, Gansu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China
^bState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Dalian 116023, Liaoning, China

Received:2024-07-18 Accepted:2024-08-26 Online:2024-11-18 Published:2024-11-10
Contact: *E-mail: Lizl@lzu.edu.cn (Z. Li),canli@dicp.ac.cn (C. Li).
Supported by:
National Natural Science Foundation of China(22072061);National Key Research and Development Program of China(2021YFA15011)

摘要/Abstract

摘要：

脲类化合物广泛存在于天然产物和合成化学品中, 可用于制造农药和医药化学品. 传统的脲合成方法主要依赖胺与光气或异氰酸酯的反应, 但这些试剂存在高毒性或腐蚀性问题, 因此亟需开发绿色环保的合成路线. 钯催化的胺氧化羰基化反应被认为是合成脲的有效方法, 但钯催化剂在反应过程中易于失活, 尤其在温和条件下生成的Pd(0)易聚集形成钯黑, 导致反应中止. 尽管引入电子转移介体(ETM)可以在一定程度上促进Pd(0)的再氧化, 但反应依然需要在高温或高压条件下进行. 因此, 开发温和条件下的催化体系是合成脲类化合物的一大挑战.

本文提出了一种光诱导胺羰基化反应, 通过光照诱导HI的再氧化, 以促进Pd(0)的再氧化为Pd(II)过程, 有效解决了Pd催化剂失活问题, 从而实现了在常温常压下高效催化各种胺的氧化羰基化, 合成多种对称及非对称脲类化合物. 在优化的反应条件下, 脂肪胺以及芳香胺都可以作为底物得到脲类目标产物, 转化率和选择性最高达到99%. 其中, 苄胺苯环取代基的给电子/吸电子效应以及位阻效应对反应活性基本没有影响, 而苯胺苯环取代基的电子效应对反应活性影响显著, 给电子取代基有利于提高反应活性. 除了合成对称脲, 该策略还可以用于非对称脲的合成, 收率最高达到98%. 此外, 该方法还可以实现克级规模的放大反应, 成功合成了一种广泛使用的抗丝虫药物乙胺嗪. 自由基捕获实验表明, 该过程中存在碘自由基和氢自由基. 通过紫外-可见光吸收光谱等方法, 结合控制实验, 研究了光照在反应机理中的作用, 结果显示在光照条件下, 碘化氢光解为碘自由基和氢自由基, 随后碘自由基自聚为碘单质, 并与Pd(0)物种反应生成活性物种PdI₂, 从而实现了催化剂的再生, 而氢自由基则与O₂反应生成H₂O.

综上, 本文开发了一种温和条件下Pd(0)再氧化为Pd(II)的策略, 并成功应用于钯催化胺羰基化合成脲类化合物, 实现了多种对称和非对称脲的合成, 并为其他钯催化的氧化反应提供了潜在应用参考. 该光促Pd(0)再氧化策略也为绿色化学合成的进一步发展提供了新思路.

关键词: 光化学, 羰基化, 钯催化, 钯再生, 脲

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

彭俊保, 解进, 李泽龙, 李灿. 光子诱导Pd催化剂的再生用于胺羰基化合成脲[J]. 催化学报, 2024, 66: 146-151.

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

图/表 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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光子诱导Pd催化剂的再生用于胺羰基化合成脲

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

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