Sonochemically-Promoted Preparation of Silica-Anchored Cyclodextrin Derivatives for Efficient Copper Catalysis

Molecules. 2019 Jul 7;24(13):2490. doi: 10.3390/molecules24132490.

Abstract

Silica-supported metallic species have emerged as valuable green-chemistry catalysts because their high efficiency enables a wide range of applications, even at industrial scales. As a consequence, the preparation of these systems needs to be finely controlled in order to achieve the desired activity. The present work presents a detailed investigation of an ultrasound-promoted synthetic protocol for the grafting of β-cyclodextrin (β-CD) onto silica. Truly, ultrasound irradiation has emerged as a fast technique for promoting efficient derivatization of a silica surface with organic moieties at low temperature. Three different β-CD silica-grafted derivatives have been obtained, and the ability of β-CD to direct and bind Cu when CD is bonded to silica has been studied. A detailed characterization has been performed using TGA, phenolphthalein titration, FT-IR, diffuse reflectance (DR), DR UV-Vis, as well as the inductively-coupled plasma (ICP) of the β-CD silica-grafted systems and the relative Cu-supported catalysts. Spectroscopic characterization monitored the different steps of the reaction, highlighting qualitative differences in the properties of amino-derivatized precursors and final products. In order to ensure that the Cu-β-CD silica catalyst is efficient and robust, its applicability in Cu(II)-catalyzed alkyne azide reactions in the absence of a reducing agent has been explored. The presence of β-CD and an amino spacer has been shown to be crucial for the reactivity of Cu(II), when supported.

Keywords: UV-visible; copper-catalysis; diffuse reflectance; green chemistry; infrared spectroscopy; organic-inorganic hybrid materials; silica; sonochemistry; β-cyclodextrin.

MeSH terms

  • Catalysis
  • Copper / chemistry*
  • Cyclodextrins / chemistry*
  • Cyclodextrins / isolation & purification*
  • Molecular Structure
  • Silicon Dioxide / chemical synthesis
  • Silicon Dioxide / chemistry*
  • Spectrum Analysis
  • Thermogravimetry

Substances

  • Cyclodextrins
  • Silicon Dioxide
  • Copper