Thermally regulated molybdate-based ionic liquids toward molecular oxygen activation for one-pot oxidative cascade catalysis,Green Chemistry

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Thermally regulated molybdate-based ionic liquids toward molecular oxygen activation for one-pot oxidative cascade catalysis
Green Chemistry ( IF 9.3 ) Pub Date : 2019-11-18 , DOI: 10.1039/c9gc03646f
Zhibin Song _{1,

2,

3,

4,

5} , Wei Huang _{1,

2,

3,

4,

5} , Yan Zhou _{1,

2,

3,

4,

5} , Zi-Qi Tian _{1,

2,

3,

4,

5} , Zhang-Min Li _{1,

2,

3,

4,

5} , Duan-Jian Tao _{1,

2,

3,

4,

5}

Affiliation

One-pot oxidative cascade catalysis plays a central role in the synthesis of key pharmaceutical and industrial molecules. Although ionic liquids are one of the most promising solvents and reaction media, the breakthrough of their catalysis in aerobic oxidation is very challenging due to the difficulty in the direct activation of molecular oxygen. Herein, a family of novel thermally regulated molybdate-based ionic liquids (Mo-ILs) has been designed and developed for the first time toward molecular oxygen activation for highly efficient tandem oxidative catalysis. Three diverse one-pot oxidative cascade processes for the syntheses of various flavones, imines, and benzyl benzoates were achieved with good to excellent yields using the Mo-IL [Bmim]₂[MoO₄] as a catalyst under air conditions. The results of spectroscopic investigations and quantum-chemical calculations further demonstrated that a thermally regulated proton migration between the cation [Bmim] and anion [MoO₄] was the key to forming N-heterocyclic carbene and thereby to effortlessly promoting the generation of ˙O₂⁻ active species from molecular oxygen, which results in excellent catalytic performance in these three aerobic tandem oxidations. Our work extends the application area of ILs as the sole catalyst to one-pot aerobic oxidative cascade catalysis, which could have pronounced implications in future work.

中文翻译：

热调节的基于钼酸盐的离子液体对分子氧的活化作用，用于一锅氧化级联催化

一锅氧化级联催化在关键药物和工业分子的合成中起着核心作用。尽管离子液体是最有前途的溶剂和反应介质之一，但由于难以直接激活分子氧，因此在有氧氧化中催化的突破非常具有挑战性。本文中，首次设计和开发了一系列新型的热调节的基于钼酸盐的离子液体（Mo-ILs），用于分子氧活化以实现高效的串联氧化催化。使用Mo-IL [Bmim] ₂ [MoO ₄ ]，可以完成三种不同的一锅氧化级联方法，用于合成各种黄酮，亚胺和苯甲酸苄酯在空气条件下作为催化剂。光谱研究和量子化学计算的结果进一步表明，阳离子[BMIM]和阴离子[的MoO之间的热调节质子迁移₄ ]的关键是形成N-杂环卡宾，从而能够毫不费力地促进0的生成₂⁻来自分子氧的活性物质，在这三个有氧串联氧化反应中具有出色的催化性能。我们的工作将作为唯一催化剂的ILs的应用领域扩展到一锅好氧氧化级联催化，这可能对未来的工作产生重大影响。

更新日期：2019-11-18

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