Double Functionalization of Alcohols via Imidate Radicals
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The Ohio State University / OhioLINK
2021
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| Online Access: | http://rave.ohiolink.edu/etdc/view?acc_num=osu1619095055361502 |
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ndltd-OhioLink-oai-etd.ohiolink.edu-osu16190950553615022021-10-02T05:10:33Z Double Functionalization of Alcohols via Imidate Radicals Prusinowski, Allen Frank Chemistry Pharmaceuticals and agrochemicals are compounds critical to improving length and quality of life. Consequently, new, innovative methods to expedite their discovery and production remain imperative targets for organic synthesis. Traditional strategies involve iterative functional group manipulations to increase molecular complexity. Although powerful, these reactive groups are sparse in contrast to the ubiquitous C-H bond, which is often the most abundant component of a molecule. As such, the direct conversion of C-H bonds to new functional groups (C-H functionalization) represents a highly impactful way to streamline the synthesis of life-changing molecules.The realization of practical C-H functionalization comes with many challenges, including the high BDE, high pKa, and difficult selectivity for reacting these groups. To address these challenges, we have implemented radical precursors that can abstract these strong bonds through thermodynamic favorability (formation of even stronger bonds). Selectivity is achieved via entropic and enthalpic favorability of the key hydrogen atom transfer (HAT) step.The research herein entails the design and development of radical-relay chaperones to selectively functionalize strong C-H bonds in alcohols. Chapter 1 introduces challenges and opportunities of C-H functionalization via radicals. Chapter 2, outlines a streamlined approach to C-H functionalization via in situ generated imidate radicals. Chapter 3 details the beta, gamma double C-H functionalization of alcohols via a radical-polar crossover cascade. And Chapter 4 shows the realization of a delta C-H functionalization of allyl alcohols by the combination of photoredox, energy transfer, and transition metal-mediated hydrogen atom transfer catalysis. Altogether, these strategies showcase the power of imidates for practical and selective C-H functionalization. 2021-10-01 English text The Ohio State University / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=osu1619095055361502 http://rave.ohiolink.edu/etdc/view?acc_num=osu1619095055361502 restricted--full text unavailable until 2022-05-11 This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws. |
| collection |
NDLTD |
| language |
English |
| sources |
NDLTD |
| topic |
Chemistry |
| spellingShingle |
Chemistry Prusinowski, Allen Frank Double Functionalization of Alcohols via Imidate Radicals |
| author |
Prusinowski, Allen Frank |
| author_facet |
Prusinowski, Allen Frank |
| author_sort |
Prusinowski, Allen Frank |
| title |
Double Functionalization of Alcohols via Imidate Radicals |
| title_short |
Double Functionalization of Alcohols via Imidate Radicals |
| title_full |
Double Functionalization of Alcohols via Imidate Radicals |
| title_fullStr |
Double Functionalization of Alcohols via Imidate Radicals |
| title_full_unstemmed |
Double Functionalization of Alcohols via Imidate Radicals |
| title_sort |
double functionalization of alcohols via imidate radicals |
| publisher |
The Ohio State University / OhioLINK |
| publishDate |
2021 |
| url |
http://rave.ohiolink.edu/etdc/view?acc_num=osu1619095055361502 |
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AT prusinowskiallenfrank doublefunctionalizationofalcoholsviaimidateradicals |
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1719486478725152768 |