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Controlled Hydrosilylations of Carbonyl Compounds and Computational Investigations of a Hydride Shuttle Mechanism for Alkene Hydrosilylation
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Chapter 1 describes tandem dual hydrosilylations of α,β-unsaturated enals. Hydrosilylations of both carbonyl compounds and alkenes have been utilized to create chiral alcohols. Tandem dual hydrosilylations (TDH) of α,β-unsaturated carbonyl compounds create five-membered oxasilacycles that can be further converted to 1,3- diols, which are a common structural motif in the polyketide natural product family. We present preliminary data and a substrate scope for the formation of these oxasilacycles en route to the 1,3-diol compounds. Chapter 2 describes hydrosilylations of esters that result in silyl acetals. The silyl acetals are chemical synthons of the corresponding aldehyde. This reaction can be coupled with a Horner-Wadsworth-Emmons reaction to create α,β-unsaturated esters in good yields. Herein we present results for a limited substrate scope of the reductive Horner-Wadsworth-Emmons reaction developed in our group. Chapter 3 describes computational support for a proposed hydride shuttle mechanism. The Jeon group recently disclosed a hydride shuttle mechanism for the regio- and diastereoselective hydrosilylation of homoallylic silyl ethers when using 3-bromocyclohexene as a coordinating ligand with a rhodium-based catalyst. Here we present a partial data set supporting the hydride shuttle mechanism over direct bond formation.