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
License
This work is licensed under a Creative Commons Attribution-NonCommercial-Share Alike 4.0 International License.
Recommended Citation
Asgari, Parham, "NEW STRATEGIES FOR CATALYTIC C-H AND OLEFIN HYDROSILYLATION" (2018). Chemistry & Biochemistry Dissertations. 256.
https://mavmatrix.uta.edu/chemistry_dissertations/256
Comments
Degree granted by The University of Texas at Arlington