Synthesis and cross-coupling reaction of alkenyl[(2-hydroxymethyl)phenyl]dimethylsilanes

Highly stable alkenyl[2-(hydroxymethyl)phenyl]dimethylsilanes are prepared by stereo- and regioselective hydrosilylation of alkynes catalyzed either by a platinum or ruthenium catalyst using protected [2-(hydroxymethyl)phenyl]dimethylsilanes. Cyclic silyl ether, 1,1-dimethyl-2-oxa-1-silaindan, also serves as a starting material for the alkenylsilanes by the ring-opening reaction with alkenyl Grignard reagents. The resulting alkenylsilanes undergo cross-coupling reaction with various aryl and alkenyl iodides under reaction conditions employing K2CO3 as a base at 35–50 °C in highly regio- and stereospecific manners. The reaction tolerates a diverse range of functional groups including silyl protections. The silicon residue is readily recovered and reused on a gram-scale synthesis. Intramolecular coordination of a proximal hydroxyl group is considered to efficiently form pentacoordinate silicates having a transferable group possibly at an axial position and, thus, responsible for the cross-coupling reaction under conditions significantly milder than those reported for the silicon-based reactions.

Graphical abstractHighly stable alkenyl[2-(hydroxymethyl)phenyl]dimethylsilanes, which are prepared by hydrosilylation of alkynes catalyzed or the reaction of 1,1-dimethyl-2-oxa-1-silaindan with alkenyl Grignard reagents, undergo cross-coupling reaction with various aryl and alkenyl iodides under reaction conditions employing K2CO3 as a base at 35–50 °C in highly regio- and stereospecific manners.Figure optionsDownload full-size imageDownload as PowerPoint slide