자료유형 | 학위논문 |
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서명/저자사항 | Method Development and Theoretical Mechanistic Elucidation of Transition Metal Mediated Radical Reactions. |
개인저자 | AbuSalim, Deyaa Isaac. |
단체저자명 | Indiana University. Chemistry. |
발행사항 | [S.l.]: Indiana University., 2019. |
발행사항 | Ann Arbor: ProQuest Dissertations & Theses, 2019. |
형태사항 | 417 p. |
기본자료 저록 | Dissertations Abstracts International 81-04B. Dissertation Abstract International |
ISBN | 9781088330715 |
학위논문주기 | Thesis (Ph.D.)--Indiana University, 2019. |
일반주기 |
Source: Dissertations Abstracts International, Volume: 81-04, Section: B.
Advisor: Cook, Silas P. |
이용제한사항 | This item must not be sold to any third party vendors.This item must not be added to any third party search indexes. |
요약 | 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. |
일반주제명 | Organic chemistry. Physical chemistry. Mechanics. Chemical reactions. |
언어 | 영어 |
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