자료유형  

 학위논문

Control Number  

0017162575

International Standard Book Number  

9798383223086

Dewey Decimal Classification Number  

540

Main Entry-Personal Name  

Sneddon, Dorian Shane.

Publication, Distribution, etc. (Imprint  

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

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2024

Physical Description  

939 p.

General Note  

Source: Dissertations Abstracts International, Volume: 86-01, Section: B.

General Note  

Advisor: Hoye, Thomas R.

Dissertation Note  

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

Summary, Etc.  

요약Since its serendipitous rediscovery in 2012, the hexadehydro-Diels-Alder (HDDA) reaction has served as a means of generating benzyne in situ via cycloisomerization of poly-yne precursors under thermal or photochemical conditions. This allows for the formation of complex benzenoid products in a single reaction step upon trapping of the insipient aryne. Aside from more fundamental mechanistic studies, my contributions to this science have fallen into three broad areas: i) formation of N-heterocycles, ii) single-step synthesis of functional materials, and iii) generation of HDDA benzynes at ambient conditions. The first area has seen extensive exploration by our lab and others; however, the latter two categories, especially the third, are still revealing interesting contemporary novelties.In my initial work, I found that trapping of HDDA benzynes with C,N-diarylimines led to a reversal in reactivity with respect to the case of classical benzynes, furnishing acridine, as opposed to phenanthridine, products (Chapter 2). Next, I trapped HDDA benzynes with arylhydrazines to form azoarenes. I then recognized that simple azobenzenes could also trap HDDA benzynes in a binary fashion that could be toggled photochemically (Chapters 3 and 4). A fundamental investigation into trapping of HDDA benzynes with electron-deficient alkenes then led to the discovery of a novel mode of strain release of ortho-annulated benzene rings (Chapter 5). Reaction of HDDA benzynes with phosphine chalcogenides revealed a new mode of aryne-aryne ligand coupling from a P(V) center (Chapter 6). Finally, diynoic acid condensation was leveraged to form anhydrides that uniquely undergo HDDA cycloisomerization below room temperature (Chapter 7).

Subject Added Entry-Topical Term  

Chemistry.

Subject Added Entry-Topical Term  

Organic chemistry.

Subject Added Entry-Topical Term  

Computational chemistry.

Subject Added Entry-Topical Term  

Materials science.

Subject Added Entry-Topical Term  

Physical chemistry.

Index Term-Uncontrolled  

Anhydrides

Index Term-Uncontrolled  

Azobenzenes

Index Term-Uncontrolled  

Benzynes

Index Term-Uncontrolled  

Hexadehydro-Diels-Alder

Index Term-Uncontrolled  

Phosphoranes

Index Term-Uncontrolled  

Strain

Added Entry-Corporate Name  

University of Minnesota Chemistry

Host Item Entry  

Dissertations Abstracts International. 86-01B.

Electronic Location and Access  

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Control Number  

joongbu:658271