Author

Parham Asgari

ORCID Identifier(s)

0000-0002-2280-0960

Graduation Semester and Year

2018

Language

English

Document Type

Dissertation

Degree Name

Doctor of Philosophy in Chemistry

Department

Chemistry and Biochemistry

First Advisor

Carl Lovely

Second Advisor

Junha Jeon

Abstract

In the works described here, new catalytic hydrosilylation strategies were explored. First, a highly selective, bond functionalization strategy, achieved via relay of two transition metal catalysts and use of traceless acetal directing groups, was introduced. Specifically, this approach involves the relay of Ir-catalyzed hydrosilylation and Rh-catalyzed ortho-C–H silylation. This acetal directing group strategy was used for catalytic ortho-C–H silylation of phenols and benzoate esters derivatives. Additionally, we developed a transition metal free, catalytic vinyl arenes hydrosilylation method. We describe our discovery on unprecedented, sustainable HAT process and report a mechanism involving Lewis base-catalyzed, complexation-induced HAT (LBCI-HAT), followed by highly selective cross-radical coupling. In this reaction, earth abundant, alkali metal Lewis base catalysts play a dual-role. They first served as a HAT initiator and subsequently a silyl radical protecting group for selective downstream processe. This efficient, and sustainable HAT permits highly controlled access to either branch-selective hydrosilylation or polymerization of vinylarenes.

Keywords

Hydrosilylation, LBCI-HAT, Hydrogen atom transfer, C-H activation

Disciplines

Chemistry | Physical Sciences and Mathematics

Comments

Degree granted by The University of Texas at Arlington

Included in

Chemistry Commons

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