Chiral mesoporous organosilicas with R-(+)-Binol integrated in the framework

Abstract

Bifunctionalized chiral mesoporous organosilicas with both R-(+)-Binol and ethylene moieties integrated in the framework was synthesized by co-condensation of 1,2-bis(trimethoxysilyl)ethane (BTME) and ( R)-2,2′-dimethoxy-6,6′-di-[(2-trimethoxysilyl)-ethenyl]-1,1′-binaphthyl ( R-MMB) in acidic medium using P123 as template for the first time. With the molar fraction of R-MMB increasing from10 to 20% in the initial mixture, the mesostructure of the material changes from a well-ordered 2D hexagonal mesostructure to a worm-like structure. The materials have a pore diameter in the range of 4.8–5.2 nm with BET surface areas varying from 356 to 894 m 2 g −1. The results of FT-IR, 13C and 29Si solid-state NMR shows the integration of the organic groups in the material though some Si–C bond cleavage was observed during the synthesis. The circular dichroism spectrum of the material dissolved in NaOH confirms that the chirality of R-(+)-Binol in the material remains unchanged compared with the molecular precursor. The hydroxyl groups of the R-(+)-Binol units were liberated by treatment of the material with BBr 3. The resultant materials were used in Ti-promoted asymmetric addition of diethylzinc to benzaldehyde. High catalytic activity (99%) with moderate enantioselectivity (39.7%) was achieved, which also confirms that R-Binol was incorporated in the PMOs successfully.