1. C-C Bond Formation via Soft Enolization and Umpolung-like Chemistry 2. Electrophilic Fluorination of Organozinc Reagents

Synthetic methodology development towards convenient C-C bond and C-F bond formation is a desirable synthetic tool for industry and academia. Using commercially available substrates towards chemical transformations is often a strategy used to simplify the process of synthesizing compounds. This dissertation focuses on the synthetic methodology development of C-C and C-F bond formation for broad applicational utility. This dissertation will discuss two synthetic strategies towards C-C bond formation, soft enolization and Umpolung-like chemistry. The direct synthesis of 1,3-diketones and β-keto thioesters using in good yields and with wide substrate tolerance was possible using our soft enolization strategy using crude acyl chlorides. Another C-C bond strategy explored was an Umpolung-like approach towards α-functionalization of ketones. Ketones are synthetically important functional group and have wide applicational uses within chemistry and biology. The α-functionalization of ketones and their derivatives via addition of their corresponding (aza) enolates to alkyl halides is a fundamental synthetic transformation but has been historically less explored despite its potential widespread utility. Our approach towards uses a novel β-silylated azoalkenes intermediate towards anti-diastereoselective α-alkylation of ketones. In addition, we explored a streamlined approach towards monofluorohydrocarbon formation via electrophilic fluorination of organozinc compounds. We hope this will have wide applicational utility as C-F bonds are important within agrochemistry and pharmaceutical chemistry.

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

2020

Author dc:creator

• Aderibigbe, Sabrina Olunike Wande

Advisor dc:contributor.advisor

• Daugulis, Olafs

Committee members dc:contributor.committeemember

• May, Jeremy A.
• Gilbertson, Scott R.
• Chen, Tai-Yen
• Ozerov, Oleg V.

• monofluorination
• soft enolization
• phenyl azoalkene
• Umpolung-like chemistry
• organozinc
• carbon-carbon bond formation
• diastereoselective

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/10657/8023

OAI identifier oai:identifier

oai:uh-ir.tdl.org:10657/8023