钌催化邻硝基苯甲醇与苄胺的转移氢化/环化反应合成喹唑啉

doi:10.6023/cjoc202503014

摘要/Abstract

报道了以N-杂环卡宾氮膦配体(CNP)螯合的钌(II)配合物为催化剂, 以邻硝基苄醇和苄胺为底物, 通过转移氢化/环化策略高效合成喹唑啉类化合物的新方法. 催化剂的CNP配体中卡宾碳的强σ给电子能力有效稳定了催化活性物种, 氮原子的半稳定性能够为反应底物分子活化提供配位空位, 两种功能的协同作用显著提升了催化效率. 在低催化剂用量的条件下, 该体系表现出优异的催化活性和选择性, 成功实现了60种不同取代喹唑啉的合成, 最高收率可达95%, 显示了广泛的底物适用性. 通过控制实验确认了苯甲醛和苯甲亚胺为该反应的关键中间体, 并证实苄胺在该反应中同时充当了氢源和氮源的双重角色.

关键词: 转移氢化/环化反应, 钌配合物, 喹唑啉

A novel method for synthesis of quinazoline through the hydrogen transfer/annulation reaction using 2-nitrobenzyl alcohol and benzylamine as starting materials is presented. The reaction is catalyzed by a ruthenium(II) complex bearing a N-heterocyclic carbene nitrogen phosphine (CNP) ligand. The pronounced α-donating capacity of the carbene within the CNP ligand of the catalyst plays a crucial role in stabilizing the catalytically active species. Additionally, the hemilability of the nitrogen facilitates the creation of coordination vacancies, which are essential for the activation of reaction substrate molecules. The synergistic interplay between these two functionalities markedly enhances catalytic efficiency. This catalytic system shows the significant catalytic activity and selectivity, along with a broad substrate adaptability. All substrates yield the target product in good to excellent yields with the maximum yield reaching 95%. Control experiments have substantiated that benzaldehyde and phenylmethanimine may serve as intermediates in the reaction, thereby reinforcing the role of benzylamine as both a hydrogen donor and a nitrogen source in the process.

Key words: hydrogen transfer/annulation reaction, ruthenium complex, quinazoline

引用此文

赵玲, 朱小慧, 陈华, 郑学丽, 薛卫超, 徐嘉麒, 付海燕, 李瑞祥. 钌催化邻硝基苯甲醇与苄胺的转移氢化/环化反应合成喹唑啉[J]. 有机化学, 2025, 45(8): 2836-2847.

Ling Zhao, Xiaohui Zhu, Hua Chen, Xueli Zheng, Weichao Xue, Jiaqi Xu, Haiyan Fu, Ruixiang Li. Synthesis of Quinazoline through Ruthenium-Catalyzed Hydrogen Transfer/Annulation Reaction between 2-Nitrobenzyl Alcohol and Benzylamine[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2836-2847.

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参考文献 17

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Entry	Deviation from the standard conditions	Yield/%
1	None	77 (65)^c
2	No base	38
3	K₃PO₄ instead of K₂HPO₄	47
4	Na₂HPO₄ instead of K₂HPO₄	51
5	DMF instead of DMSO	67
6	o-Xylene instead of DMSO	50
7	PhCl instead of DMSO	48
8	120 ℃	54
9	κ³-CNP-Ru instead of κ²-CP-Ru	75
10	[RuH(CO)(PPh₃)₃Cl instead of κ²-CP-Ru	49

Entry	Deviation from the standard conditions	Yield/%
1	None	77 (65)^c
2	No base	38
3	K₃PO₄ instead of K₂HPO₄	47
4	Na₂HPO₄ instead of K₂HPO₄	51
5	DMF instead of DMSO	67
6	o-Xylene instead of DMSO	50
7	PhCl instead of DMSO	48
8	120 ℃	54
9	κ³-CNP-Ru instead of κ²-CP-Ru	75
10	[RuH(CO)(PPh₃)₃Cl instead of κ²-CP-Ru	49