TY - JOUR
T1 - Sonochemically-promoted preparation of silica-anchored cyclodextrin derivatives for efficient copper catalysis
AU - Martina, Katia
AU - Calsolaro, Federica
AU - Zuliani, Alessio
AU - Berlier, Gloria
AU - Chávez-Rivas, Fernando
AU - Moran, Maria Jesus
AU - Luque, Rafael
AU - Cravotto, Giancarlo
N1 - Publisher Copyright:
© 2019 by the authors
PY - 2019
Y1 - 2019
N2 - 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.
AB - 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.
KW - Copper-catalysis
KW - Diffuse reflectance
KW - Green chemistry
KW - Infrared spectroscopy
KW - Organic-inorganic hybrid materials
KW - Silica
KW - Sonochemistry
KW - UV-visible
KW - β-cyclodextrin
UR - http://www.scopus.com/inward/record.url?scp=85068675100&partnerID=8YFLogxK
U2 - 10.3390/molecules24132490
DO - 10.3390/molecules24132490
M3 - Artículo
C2 - 31284697
SN - 1420-3049
VL - 24
JO - Molecules
JF - Molecules
IS - 13
M1 - 2490
ER -