Synthesis and Transformations of Functionalized Benzosiloxaboroles

Abstract

The synthesis and characterization of a series of fluorinated benzosiloxaboroles bearing synthetically useful formyl and cyano groups is reported. These compounds have been obtained by multistep syntheses starting with simple halogenated benzenes. The general synthetic protocol was based on the generation of ortho‐boronated aryldimethylsilanes which undergo dehydrogenative cyclization upon hydrolytic workup due to activation of the Si–H bond by the adjacent boronic group. In some cases the synergy of adjacent boron‐ and silicon‐based functionalities resulted in an unexpected hydrosilylation of the CHO group under mild aqueous conditions. The reduction of a benzosiloxaborole derivative bearing the formyl group at the ortho position with respect to the boron atom resulted in a structural transformation reflecting the higher stability of the carboxaborole heterocycle with respect to its silicon counterpart. Thus, a unique heterocyclic system featuring a central 10‐membered ring comprising two borasiloxane linkages was isolated.

Introduction of Boron Functionalities into Silsesquioxanes: Novel Independent Methodologies

“…The conversion and purity of obtained compounds wasd etermined by NMR spectroscopy, in particular by 29 Si NMR spectroscopy. The conversion and purity of obtained compounds wasd etermined by NMR spectroscopy, in particular by 29 Si NMR spectroscopy.…”

“…The structure of products was determined by NMR spectroscopy.T he spectra 1 H, 13 Ca nd 29 Si NMR were recorded on the Bruker ASCEND 400 (400 MHz) spectrometer using C 6 D 6 as the solvent. POSS compounds were obtained from Hybrid Plastics.…”

“…[9][10][11][12] Recently,t he synthesis of functionalizeds ilsesquioxanes cages( SQs) containing other heteroatomsa nd functional groupsh as been strongly developed by many scientists. [23][24][25][26][27][28] On the other hand, the boron modification of variousc ompounds, [29][30][31][32][33] polymers, [34,35] and nanoparticles is attractivef or aw ide range of applications. [23][24][25][26][27][28] On the other hand, the boron modification of variousc ompounds, [29][30][31][32][33] polymers, [34,35] and nanoparticles is attractivef or aw ide range of applications.…”

“…Traditionally, conventional methods using halo‐compounds are used to modify their structure, however catalytic solutions are becoming increasingly investigated . On the other hand, the boron modification of various compounds, polymers, and nanoparticles is attractive for a wide range of applications . Si‐ O ‐B moiety, which is a core of poly(borasiloxane)s, is very interesting in terms of modern polymer chemistry .…”

Differential Sensing of Saccharides Based on an Array of Fluorinated Benzosiloxaborole Receptors

“…Recently, the synthesis and comprehensive characterization of benzosiloxaboroles bearing various functional groups such as halogens (X = F, Cl, Br), CHO, CH 2 OH, B(OH) 2 was reported [ 11 ]. Antimicrobial activity of those derivatives was evaluated, and the structure–properties relationships were discussed.…”