BINOL-Catalyzed Asymmetric Synthesis of Chiral Heterocycles; Experimental Mechanistic Study of Binol-Catalyzed Conjugate Addition of Vinylboronic Acids to Enones; Enantioselective Synthesis of Diarylalkane Compounds via Binol-Catalyzed Conjugate Addition

A BINOL-catalyzed conjugate addition was shown in our laboratory to be compatible with unprotected indole substrates. This was considered to be an advantage over typical organometallic strategies since it allowed the use of mild boron-based nucleophiles. With this well established method, we investigated the synthesis of a variety of chiral heterocyclic compounds. A new method was developed showing great compatibility with different heteroaryl structures. Along with that, a new BINOL catalyst was introduced that exhibited superior catalytic activity to previously used catalysts. As proposed for previous studies, the rate determining step of the transformation was the carbon-carbon bond formation. In another project, we carried out a Hammet plot study to investigate the electronic effects of the aryl groups on the reaction rate. The results provided solid support for the proposal mentioned above. Work in our laboratory showed that heteroaryltrifluoroborates exhibited superior reactivity to boronic acids in the synthesis of chiral bis-heterocycles. Therefore, in the latest project, we made use of aryltrifluoroborates in BINOL catalysis to construct different chiral bis-aryl compounds, whose structures were present in a number of important molecules. As a result, a new strategy was successfully established allowing access to a variety of enantioenriched diarylalkanes.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

Doctoral

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Houston

Year dc:date.issued

2015

Author dc:creator

• Nguyen, Thien Si 1986-

Advisor dc:contributor.advisor

• May, Jeremy A.

Committee members dc:contributor.committeemember

• Daugulis, Olafs
• Coltart, Don M.
• Halasyamani, P. Shiv
• McMurray, John S.

• BINOL catalysis, organocatalysis, enantioselective, heterocycles, bi-aryl compounds, mechanism.

Statement dc:rights

• The author of this work is the copyright owner. UH Libraries and the Texas Digital Library have their permission to store and provide access to this work. UH Libraries has secured permission to reproduce any and all previously published materials contained in the work. Further transmission, reproduction, or presentation of this work is prohibited except with permission of the author(s).

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/10657/6549

OAI identifier oai:identifier

oai:uh-ir.tdl.org:10657/6549