| Allyl and vinylsilanes are important nucleophiles in organic synthesis.They are stable reagents that can participate in a variety of transformations including mainly Hosomi-Sakurai crotylations, Hiyama-Denmark cross couplings, Tamao-Fleming oxidations, and fluorination reactions. Prior to this work there were few methods that allowed for the synthesis of these valuable compounds from simple alkenes. Using transition metal catalysis, I sought to develop a method to access unsaturated organosilanes using a reaction analogous to the Heck reaction. This endeavor proved valuable, as a powerful new method was developed that allows for the synthesis of vinylsilanes from styrenes and related molecules, and the synthesis of allylsilanes from simple ?-olefins containing allylic hydrogen atoms. The latter reaction is highly selective for the linear E-allylsilane.;This thesis describes the initial discovery and optimization of the silyl-Heck reaction using palladium catalysis. Methods were developed for use of silyl iodides or silyl chlorides with lithium iodide additives as coupling reagents. The design and synthesis of second-generation ligands have allowed for the synthesis of allylsilanes in high yield by overcoming alkene isomerization. With these ligands I have identified a simplified method to prepare vinyl and allylsilanes. The general transformation has been expanded to nickel catalysis,... |
