자료유형  

 학위논문

Control Number  

0017160256

International Standard Book Number  

9798384097662

Dewey Decimal Classification Number  

540

Main Entry-Personal Name  

Xu, Qian.

Publication, Distribution, etc. (Imprint  

[S.l.] : University of Minnesota., 2024

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2024

Physical Description  

450 p.

General Note  

Source: Dissertations Abstracts International, Volume: 86-03, Section: B.

General Note  

Advisor: Hoye, Thomas R.

Dissertation Note  

Thesis (Ph.D.)--University of Minnesota, 2024.

Summary, Etc.  

요약Reactive intermediates are highly reactive molecules featured by having short lifetimes. Their generations, structures, and reactivities are essential to the field of chemistry and have been attracting increasing attention. More often than not, the generation of a reactive intermediate invokes the use of catalysts, reagents, additives or irradiation. Direct generation of reactive intermediates under thermal, uncatalyzed, reagent- additive-free conditions remains a less explored but attractive strategy. The simple and straightforward setup of thermal reactions make it cost-efficient, reproducible, scalable, and practical for synthesis. More importantly, it also provides a platform for the discovery of novel reactivities and enables the construction of complex molecules. An alkyne is a particularly interesting functional group that can be further converted into reactive intermediates. On the one hand, alkynes generally have ample kinetic stability to render them easy to prepare, easy to handle, and shelf-stability that makes many of them commercially available. On the other, alkynes have inherently weak pi-bonds that can provide considerable favorable enthalpic contribution when they participate in a transformation, which can be a pivotal thermodynamic driving force for a thermal reaction. Furthermore, the high degree of unsaturation of an alkyne confers versatile modes of reactivities between alkynes and their reaction partners. These features synergistically make alkynes ideal precursors to reactive intermediates. Yet there remains a gap between alkynes and reactive intermediates, cycloaddition reactions provide a potential bridge for commuting. In this document, I will demonstrate how thermal, additive-free cycloaddition approaches convert alkynes into reactive intermediates including: i) strained reactive intermediates such as benzynes, 1,2,4-cyclohexatrienes, and 6-aza-1,2,4-cylcohexatrienes; ii) bond-deficient reactive intermediates such, a,3-dehydrotoluenes (DHTs), and free carbenes. DFT computations have provided crucial guidance for the reaction design and revealed valuable mechanistic insights across my entire research.

Subject Added Entry-Topical Term  

Chemistry.

Subject Added Entry-Topical Term  

Thermodynamics.

Subject Added Entry-Topical Term  

Analytical chemistry.

Subject Added Entry-Topical Term  

Organic chemistry.

Index Term-Uncontrolled  

Cycloaddition reactions

Index Term-Uncontrolled  

Alkynes

Index Term-Uncontrolled  

Reactive intermediates

Index Term-Uncontrolled  

Thermal reaction

Index Term-Uncontrolled  

Carbene

Added Entry-Corporate Name  

University of Minnesota Chemistry

Host Item Entry  

Dissertations Abstracts International. 86-03B.

Electronic Location and Access  

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Control Number  

joongbu:654073