Allylic oxidation of olefins with a manganese-based metal–organic framework,Green Chemistry

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Allylic oxidation of olefins with a manganese-based metal–organic framework
Green Chemistry ( IF 9.3 ) Pub Date : 2019-05-29 , DOI: 10.1039/c9gc01337g
Jingwen Chen _{1,

2,

3,

4,

5} , Minda Chen _{6,

7,

8,

9} , Biying Zhang _{6,

7,

8,

9} , Renfeng Nie _{6,

7,

8,

9,

10} , Ao Huang _{6,

7,

8,

9} , Tian Wei Goh _{6,

7,

8,

9,

11} , Alexander Volkov _{6,

7,

8,

9} , Zhiguo Zhang _{1,

2,

3,

4,

5} , Qilong Ren _{1,

2,

3,

4,

5} , Wenyu Huang _{6,

7,

8,

9,

11}

Affiliation

Selective oxidation of olefins to α,β-unsaturated ketones under mild reaction conditions has attracted considerable interest, since α,β-unsaturated ketones can serve as synthetic precursors for various downstream chemical products. The major inherent challenges with this chemical oxidation are chemo- and regio-selectivity as well as environmental concerns, i.e. catalyst recycle, safety and cost. Using atmospheric oxygen as an environmentally friendly oxidant, we found that a metal–organic framework (MOF) constructed with Mn and a tetrazolate ligand (CPF-5) showed good activity and selectivity for the allylic oxidation of olefins to α,β-unsaturated ketones. Under the optimized conditions, we could achieve 98% conversion of cyclohexene and 87% selectivity toward cyclohexanone. The combination of a substoichiometric amount of TBHP (tert-butylhydroperoxide) and oxygen not only provides a cost effective oxidation system but significantly enhances the selectivity to α,β-unsaturated ketones, outperforming most reported oxidation methods. This catalytic system is heterogeneous in nature, and CPF-5 could be reused at least five times without a significant decrease in its catalytic activity and selectivity.

中文翻译：

锰基金属-有机骨架对烯烃的烯丙基氧化

在温和的反应条件下，烯烃选择性氧化为α，β-不饱和酮引起了人们的极大兴趣，因为α，β-不饱和酮可以用作各种下游化学产品的合成前体。这种化学氧化的主要内在挑战是化学和区域选择性以及对环境的关注，即催化剂的循环利用，安全性和成本。使用大气中的氧气作为环境友好型氧化剂，我们发现由Mn和四唑酸酯配体（CPF-5）构成的金属有机骨架（MOF）对于烯烃烯丙基氧化为α，β-不饱和酮表现出良好的活性和选择性。。在优化的条件下，我们可以实现98％的环己烯转化率和87％的对环己酮选择性。亚化学计量的TBHP（叔-氢过氧化物和氧气不仅提供了一种经济高效的氧化系统，而且显着提高了对α，β-不饱和酮的选择性，优于大多数报道的氧化方法。该催化体系本质上是多相的，CPF-5可以重复使用至少五次，而其催化活性和选择性不会显着降低。

更新日期：2019-07-01

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