Palladium catalyzed cross-coupling of silicon reagents for the formation of allylsilanes, vinylsilanes, and tetrasubstituted alkenes
Date
2020
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Publisher
University of Delaware
Abstract
Organosilanes are an important class of substrates in organic synthesis. In particular, allyl- and vinyl-silanes are important intermediates in a variety of reactions. Due to their high utility, methods for their preparation are of high interest. This thesis describes the development of simplified conditions for the conversion of simple, terminal alkenes to allyl- and vinyl-silanes. Through mechanistic analysis of palladium-complexes through-out the reaction, conditions were developed using readily available and bench stable pre-catalysts, which enhances the utility of the reaction. ☐ Although the silyl-Heck reaction allows for the simple preparation of vinylsilanes, the formation of tetrasubstituted vinylsilanes remained a challenge. Chapter 4 of this thesis describes the development of a multicomponent carbosilylation reaction, which allows for the formation of tetrasubstituted vinylsilanes directly from simple alkyne starting materials. The development and mechanistic considerations of this reaction will be discussed. ☐ Vinylsilanes are important intermediates towards the formation of stereodefined alkenes through Hiyama cross-coupling reactions; however, methods for the cross-coupling of tetrasubstituted vinylsilanes are extremely limited. Chapter 5 of this thesis details the development of conditions for the Hiyama cross-coupling of these highly-substituted vinylsilanes to form stereodefined tetrasubstituted alkenes.
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Keywords
Allylsilane, Catalysis, Cross-coupling, Hiyama, Silyl-Heck, Vinylsilane