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香港科技大学-1金属有机框架作为一种高效双功能催化剂:用于形成具有碳-碳、碳-氮、碳-硫和碳-氧键的β-芳基磺酰胺的氮杂环丙烷化和一锅开环转化

HKUST-1 Metal Organic Framework as an Efficient Dual-Function Catalyst: Aziridination and One-Pot Ring-Opening Transformation for Formation of β-Aryl Sulfonamides with C-C, C-N, C-S, and C-O Bonds.

作者信息

Sharma Debesh, Rasaily Sagarmani, Pradhan Sajan, Baruah Khanindram, Tamang Sudarsan, Pariyar Anand

机构信息

Department of Chemistry, Sikkim University, Tadong, 737102 Gangtok, East Sikkim, India.

出版信息

Inorg Chem. 2021 Jun 7;60(11):7794-7802. doi: 10.1021/acs.inorgchem.1c00201. Epub 2021 May 11.

Abstract

Metal-organic frameworks (MOFs) are extensively used in catalysis due to their robust structure, well-defined periodic reaction centers, and high porosity. We report Cu(BTC)·(HO) (HKUST-1) as an efficient heterogeneous catalyst for aziridination of alkene and ring-opening reaction of activated aziridines. Furthermore, we demonstrate that the transfer of a nitrogen group from PhINTs to olefins and its analogue to give aziridines takes place at the coordinatively unsaturated Cu(II) site of Cu(BTC)-MOF; however, the ring opening of activated aziridines is controlled by the Cu(II) Lewis acid site, and generation of coordinative unsaturation by thermal activation of the MOF is not necessarily important. The key advantage of this catalytic approach is the direct formation of C-C, C-N, C-O, and C-S bonds yielding β-aryl sulfonamide derivatives through a simultaneous aziridination ring-opening reaction of the alkene in one pot using a single catalyst.

摘要

金属有机框架材料(MOFs)因其坚固的结构、明确的周期性反应中心和高孔隙率而被广泛应用于催化领域。我们报道了Cu(BTC)·(H₂O)(HKUST-1)作为一种高效的非均相催化剂,用于烯烃的氮杂环丙烷化反应和活性氮杂环丙烷的开环反应。此外,我们证明了从苯磺酰亚胺氮宾(PhINTs)到烯烃及其类似物的氮基团转移以生成氮杂环丙烷是在Cu(BTC)-MOF的配位不饱和Cu(II)位点上发生的;然而,活性氮杂环丙烷的开环反应是由Cu(II)路易斯酸位点控制的,并且通过MOF的热活化产生配位不饱和并不一定重要。这种催化方法的关键优势在于通过使用单一催化剂在一个反应釜中同时进行烯烃的氮杂环丙烷化开环反应,直接形成C-C、C-N、C-O和C-S键,生成β-芳基磺酰胺衍生物。

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