Controlling the selectivity of competitive nitroaldol condensation by using a bifunctionalized mesoporous silica nanosphere-based catalytic system.
A series of bifunctionalized mesoporous silica nanosphere-based (MSN) heterogeneous catalysts for the nitroaldol (Henry) reaction have been synthesized. A common 3-[2-(2-aminoethylamino)ethylamino]propyl (AEP) primary group and three different secondary groups, ureidopropyl (UDP), mercaptopropyl (MP), and allyl (AL) functionalities, were incorporated to these mesoporous silica materials by introducing equal amounts of AEP-trimethoxysilane with UDP-, MP-, or AL-trialkoxysilane precursors to our previously reported co-condensation reaction. Structures and relative concentrations of the functional groups were detailed by solid-state NMR and other spectroscopic techniques. The AEP group served as a catalyst, and the other secondary groups provided different noncovalent interactions to reactants and thereby controlled the reaction selectivity. By varying the secondary group in these bifunctionalized MSN catalysts, we investigated the selectivity of a nitroaldol reaction of two competing benzaldehydes reacting with nitromethane by measuring the molar ratio of the nitroalkene products. The selectivity of the bifunctionalized MSN catalysts could be systematically tuned simply by varying the physicochemical properties of the pore surface-bound secondary groups, i.e., polarity and hydrophobicity.
Huh
Seong
S
Department of Chemistry and Ames Laboratory, Iowa State University, Ames, Iowa 50011, USA.
Chen
Hung-Ting
HT
Wiench
Jerzy W
JW
Pruski
Marek
M
Lin
Victor S-Y
VS