Recent advances in heteroatomic-Heck reactions towards the synthesis of unsaturated silanes and boronic esters

Abstract

Unsaturated heteroatomic compounds are an important class of molecules in many disciplines of chemistry. In particular, organosilanes and boronic esters serve as valued reagents and intermediates in the synthesis of complicated organic materials. Because of their high synthetic value, much interest has been payed towards the synthesis of these unique reagents. This thesis details my endeavors towards discovering new synthetic routes to unsaturated organo silanes and boronic esters. I assisted in the development of a nickel catalyzed methods for the silylation of aromatic alkenes with various different electrophilic silyl-triflate reagents. My studies of the intramolecular silyl-Heck reaction resulted in several new discoveries including the first examples of silylation of disubstituted alkenes. Computational investigation into the mechanism of the silyl-Heck reaction led to a better and more complete understanding of the inter- and intramolecular reaction pathways. My work involving boron electrophiles in Heck reactions resulted in the first boryl-Heck reaction published in the Journal of the American Chemical Society. Follow up studies increased the reactivity of the catalytic system allowing for the synthesis of trisubstituted alkenyl boronic esters from disubstituted and internal alkenes. During these studies, several new and related reactions were discovered and are detailed in the appendix of this thesis, some of which are currently being investigated.