Hydrosilylation of Arynes with Silanes and Silicon‐Based Polymer

Abstract

AbstractBenzyne derived from hexadehydrogenated Diels Alder (HDDA) reactions was found to be an efficient hydrosilylation acceptors. Various silanes can react smoothly with HDDA‐derived benzyne to give the arylation products. Lewis acid such as boron trifluoride etherate can accelerate these hydrosilylation reactions. Polyhydromethylsiloxane (PHMS), a widely used organosilicon polymer, was also successfully modified using our method. About 5 % of Si−H bonds in the polymer were inserted by benzynes, giving a functional PHMS with much more solubility in methanol and with a blue‐emitting fluorescence behavior. Mechanism research shows that the insertion of benzyne into the Si−H bond probably undergoes a synergistic pathway, which is quite different from the traditional radical‐initiated hydrosilylation or transition‐metal‐catalyzed hydrosilylation.