有机膦催化下氨(羟)基取代的α,β-不饱和酯(酮)与异(硫)氰酸酯的[3+2]和[4+2]环加成反应

doi:10.6023/cjoc202604009

研究论文

有机膦催化下氨(羟)基取代的α,β-不饱和酯(酮)与异(硫)氰酸酯的[3+2]和[4+2]环加成反应

胡燚^†, 蔡逸飞^†, 高浩杰^†, 姜磬歌, 刘明国, 王能中^*, 黄年玉^*

三峡大学生物与制药学院天然产物研究与利用湖北省重点实验室湖北宜昌 443002

收稿日期:2026-06-16 修回日期:2026-07-14
作者简介:^†共同第一作者
基金资助:
111引智基地(D20015)、湖北省自然科学基金宜昌创新发展联合基金重点项目(2025AFD262)、湖北省中央引导地方科技发展资金项目(2024BSB016).

Phosphine-Catalyzed [3+2] and [4+2] Annulations of Amino(Hydroxyl)-Substituted α,β-Unsaturated Esters(Ketones) with Iso(thio)cyanates

Hu, Yi^†, Cai, Yifei^†, Gao, Haojie^†, Jiang, qingge, Liu, Mingguo, Wang, Nengzhong^*, Huang, Nianyu^*

Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang Hubei 443002

Received:2026-06-16 Revised:2026-07-14
About author:^†These authors contributed equally to this work.
Supported by:
111 Project (No. D20015), the Hubei Provincial Natural Science Foundation Joint Fund for Innovation and Development Project of Yichang (2025AFD262), and the Hubei Provincial Central Government Guided Local Science and Technology Development Project (2024BSB016).

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摘要/Abstract

多杂原子五、六元饱和环状化合物广泛存在于天然产物与药物分子中, 具备优良的生物活性, 其骨架构建是有机合成领域的研究热点. 目前该类不同骨架化合物需采用不同方法合成, 整体合成效率偏低. 本文报道一种通过有机膦催化下氨(羟)基取代的α,β-不饱和酯(酮)与异(硫)氰酸酯的[3+2]和[4+2]环加成反应, 实现咪(噁)唑烷(硫)酮、四氢嘧啶酮和噁嗪烷酮类化合物的多样性发散式高效合成. 该方法具有操作简便、底物适用范围广、100%原子利用率等优点. 此外, 克级规模合成及衍生化反应表明该方法具有较好的应用价值.

关键词: 有机膦催化, 环加成反应, 咪唑烷酮, 四氢嘧啶酮, 噁嗪烷酮

Five- and six-membered saturated polyheterocyclic compounds are widely found in natural products and pharmaceuticals with excellent biological activities. These scaffolds have attracted significant attention in organic synthesis. However, constructing these scaffolds typically requires different approaches, resulting in low synthetic efficiency. This paper reports a novel method for the efficient divergent synthesis of imidazolidinones, oxazolidinones, imidazolidinethiones, oxazolidinethiones tetrahydropyrimidinones, and oxazinanones via phosphine-catalyzed [3+2] and [4+2] annulations of amino (hydroxyl)-substituted α,β-unsaturated esters (ketones) with iso(thio)cyanates. This method offers advantages such as simple operation, broad substrate scope, and 100% atom economy. Gram-scale synthesis and further transformations demonstrate its good application potential.

Key words: phosphine catalysis, annulation, imidazolidinone, tetrahydropyrimidinone, oxazinanone

引用此文

胡燚, 蔡逸飞, 高浩杰, 姜磬歌, 刘明国, 王能中, 黄年玉. 有机膦催化下氨(羟)基取代的α,β-不饱和酯(酮)与异(硫)氰酸酯的[3+2]和[4+2]环加成反应[J]. 有机化学, doi: 10.6023/cjoc202604009.

Hu, Yi, Cai, Yifei, Gao, Haojie, Jiang, qingge, Liu, Mingguo, Wang, Nengzhong, Huang, Nianyu. Phosphine-Catalyzed [3+2] and [4+2] Annulations of Amino(Hydroxyl)-Substituted α,β-Unsaturated Esters(Ketones) with Iso(thio)cyanates[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202604009.

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