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020 ▼a 9781088330715
035 ▼a (MiAaPQ)AAI13904160
040 ▼a MiAaPQ ▼c MiAaPQ ▼d 247004
0820 ▼a 540
1001 ▼a AbuSalim, Deyaa Isaac.
24510 ▼a Method Development and Theoretical Mechanistic Elucidation of Transition Metal Mediated Radical Reactions.
260 ▼a [S.l.]: ▼b Indiana University., ▼c 2019.
260 1 ▼a Ann Arbor: ▼b ProQuest Dissertations & Theses, ▼c 2019.
300 ▼a 417 p.
500 ▼a Source: Dissertations Abstracts International, Volume: 81-04, Section: B.
500 ▼a Advisor: Cook, Silas P.
5021 ▼a Thesis (Ph.D.)--Indiana University, 2019.
506 ▼a This item must not be sold to any third party vendors.
506 ▼a This item must not be added to any third party search indexes.
520 ▼a Radical transition metal mediated reactions offer important and complementary reactivity to two electron methodologies. The design of these reactions relies on important advances in bench chemistry and detailed mechanistic understanding of their operative mechanisms, usually aided by thorough theoretical studies. We demonstrated the development of a series of palladium-catalyzed alkyne insertion reactions of alkyl iodides to produce tetrasubstituted olefins. These reactions include: (i) an insertion/cyanation to produce 慣,棺 unsaturated nitriles, (ii) an insertion/carbonylative esterification to produce 慣棺 unsaturated methyl esters, and (iii) an alkyne insertion/borylation to produce vinyl boronic esters. The reactions proceed in good yields and present a mild route to access the corresponding manifolds. Additionally, we employed DFT in a series of detailed studies to elucidate the mechanism of several transition metal mediated transformations to understand their pathways and shine light on the origin of their regio- and stereo- selectivity. These studies focused on identifying and comparing inner sphere and outer sphere mechanisms in: (i) Pd-catalyzed alkyne insertion reactions, (ii) Pd-catalyzed regio-divergent arylations of triazolopyridine systems, (iii) Fe-catalyzed fluorine transfer reactions of fluoroamides, and (iv) Cu-mediated C-H trifluoromethylation and alkyne bis-trifluoromethylation reactions with Grushin's bpyCu(CF3)3 reagent.
590 ▼a School code: 0093.
650 4 ▼a Organic chemistry.
650 4 ▼a Physical chemistry.
650 4 ▼a Mechanics.
650 4 ▼a Chemical reactions.
690 ▼a 0490
690 ▼a 0494
71020 ▼a Indiana University. ▼b Chemistry.
7730 ▼t Dissertations Abstracts International ▼g 81-04B.
773 ▼t Dissertation Abstract International
790 ▼a 0093
791 ▼a Ph.D.
792 ▼a 2019
793 ▼a English
85640 ▼u http://www.riss.kr/pdu/ddodLink.do?id=T15492517 ▼n KERIS ▼z 이 자료의 원문은 한국교육학술정보원에서 제공합니다.
980 ▼a 202002 ▼f 2020
990 ▼a ***1008102
991 ▼a E-BOOK