Controlled Hydrosilylations of Carbonyl Compounds and Computational Investigations of a Hydride Shuttle Mechanism for Alkene Hydrosilylation

Author

Gabriela Trog

Graduation Semester and Year

2015

Language

English

Document Type

Thesis

Degree Name

Master of Science in Chemistry

Department

Chemistry and Biochemistry

First Advisor

Junha Jeon

Abstract

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.

Keywords

Hydrosilylation, Catalysis, Reductive olefination, Computational chemistry

Disciplines

Chemistry | Physical Sciences and Mathematics

License

This work is licensed under a Creative Commons Attribution-NonCommercial-Share Alike 4.0 International License.

Comments

Degree granted by The University of Texas at Arlington

Recommended Citation

Trog, Gabriela, "Controlled Hydrosilylations of Carbonyl Compounds and Computational Investigations of a Hydride Shuttle Mechanism for Alkene Hydrosilylation" (2015). Chemistry & Biochemistry Theses. 96.
https://mavmatrix.uta.edu/chemistry_theses/96