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Nanosheet-enhanced efficiency in amine-catalyzed asymmetric epoxidation of α, β-unsaturated aldehydes via host-guest synergy
Molecular Catalysis ( IF 4.6 ) Pub Date : 2017-10-09 , DOI: 10.1016/j.mcat.2017.09.035
Hui Liu , Zhe An , Jing He

Amine-catalyzed asymmetric epoxidation of α, β-unsaturated aldehydes has been promoted by attaching the nanosheets of layered double hydroxides (LDHs), a natural and/or synthetic anionic layered compound. 76% of epoxide yield and 93% ee of major diastereomer have been afforded in the asymmetric epoxidation of cinnamaldehyde. The amine sites employed here are the amino group in α-amino acid anion intercalated in the interlayer space of LDHs. The nanosheets of LDHs have been revealed to play key role in the enhancement of catalytic activity by affording the desired basicity and the boost of enantioselectivity by serving as the rigid substituent of amino acids. The hydrophobic interlayer microenvironment and ordered arrangement of intercalated amino acid anions additionally contribute to the catalytic efficacy. Stronger interlayer hydrophobicity favors the conversion and epoxide yield and better arrangement of interlayer anions favors the ee.



中文翻译:

通过主体-客体协同作用提高胺,α,β-不饱和醛在胺催化的不对称环氧化中的纳米片增强效率

胺催化的α,β不对称环氧化通过附着层状双氢氧化物(LDH)的纳米片(天然和/或合成阴离子层状化合物),可以促进不饱和醛的形成。肉桂醛的不对称环氧化提供了76%的环氧化物收率和93%ee的主要非对映异构体。这里使用的胺位点是插入在LDHs的层间空间中的α-氨基酸阴离子中的氨基。已经揭示出LDHs的纳米片通过提供所需的碱性和通过用作氨基酸的刚性取代基而在催化活性的增强中起关键作用。疏水层间微环境和插层氨基酸阴离子的有序排列另外有助于催化效力。

更新日期:2017-10-09
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