2026-09-20T11:42:09Zhttps://ecommons.cornell.edu/server/oai/requestoai:ecommons.cornell.edu:1813/516172026-05-15T19:50:35Zcom_1813_35col_1813_47
Hein, Samuel Jay
Dichtel, William R
Coates, Geoff
Ober, Christopher K
2017-07-07T12:48:40Z
2017-07-07T12:48:40Z
2017-05-30
ProQuest Submission ID: 10304
ProQuest Publication ID: 10279730
https://hdl.handle.net/1813/51617
https://doi.org/10.7298/X46D5R3M
9948840
This dissertation describes recent advances in methodology to access novel aromatic architectures using a benzannulation strategy (Chapter 1). Silyl protected acetylenes are readily reacted to yield the corresponding 2-naphthylsilane. These compounds serve as synthetically useful building blocks for further derivatization and iterative benzannulation to access sterically crowded substrates (Chapter 2). Despite the high efficiency of this reaction, phenylene ethynylene macrocycles prove to be too rigid to undergo complete benzannulation (Chapter 3). Finally, the scope of this transformation was expanded beyond aryl substituted acetylenes with the benzannulation of silyl-haloacetylenes (Chapter 4). These products readily generate 2-naphthynes with the addition of cesium fluoride and can be oligomerized or cyclized to isolate substituted ortho-naphthalenes. Through our fundamental studies into this transformation, we have shown it serves as a versatile reaction in the organic synthetic chemists toolbox to access novel aromatic architectures.
en_US
aromatic
Graphene
organic
Benzannulation
PAH
Polymer
Organic chemistry
The Synthesis of Naphthalene-Containing Compounds and Materials Using Benzannulation Reactions
dissertation or thesis
application/pdf
Chemistry and Chemical Biology
Cornell University
Doctor of Philosophy
Ph. D., Chemistry and Chemical Biology
https://hdl.handle.net/1813/59810
Publication
Cornell Theses and Dissertations
Hein, Samuel Jay
5893a6ea-7af3-41d7-abc6-04bcd26ab5df
open.access
open.access
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<Keyword>aromatic</Keyword>
<Keyword>Graphene</Keyword>
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<Keyword>Benzannulation</Keyword>
<Keyword>PAH</Keyword>
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<Abstract>This dissertation describes recent advances in methodology to access novel aromatic architectures using a benzannulation strategy (Chapter 1). Silyl protected acetylenes are readily reacted to yield the corresponding 2-naphthylsilane. These compounds serve as synthetically useful building blocks for further derivatization and iterative benzannulation to access sterically crowded substrates (Chapter 2). Despite the high efficiency of this reaction, phenylene ethynylene macrocycles prove to be too rigid to undergo complete benzannulation (Chapter 3). Finally, the scope of this transformation was expanded beyond aryl substituted acetylenes with the benzannulation of silyl-haloacetylenes (Chapter 4). These products readily generate 2-naphthynes with the addition of cesium fluoride and can be oligomerized or cyclized to isolate substituted ortho-naphthalenes. Through our fundamental studies into this transformation, we have shown it serves as a versatile reaction in the organic synthetic chemists toolbox to access novel aromatic architectures.</Abstract>
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