Semester

Spring

Date of Graduation

2013

Document Type

Thesis

Degree Type

MS

College

Eberly College of Arts and Sciences

Department

Chemistry

Committee Chair

Kung K Wang

Committee Co-Chair

Jeffrey L Petersen

Committee Member

Bjoern C Soederberg

Abstract

Bowl-shaped and basket-shaped polycyclic aromatic hydrocarbons (PAHs) have attracted considerable attention in recent years. They are challenging targets for total synthesis due to the presence of substantial strain energy in the curved structures. A solution-phase synthesis of a bowl-shaped polycyclic aromatic hydrocarbon C27H12 was explored. The use of the casecade radical cyclization reactions of a benzannulated enyne-allene is a key feature of this synthetic pathway. The mild reaction conditions provide efficient and flexible designs for bowl-shaped and basked-shaped PAHs and their precursors. Our proposed synthesis strategy for the bowl-shaped C27H12 involves an initial synthesis of a benzannulated enediynyl propargylic alcohols followed by the cascade cyclization reactions of the resulting enyne-allenes. The use of the palladium-catalyzed intramoleular arylation reactions is proposed as a key step leading to the final products. Specifically, transformation of 1-indanone to a key intermediate, 2-methoxy-2-(2- methoxyethyl)-1-indanone, was extensively investigated, and the conditions for forming 1-(2-ethynylphenyl)-2-(2,6-dichlorophenyl)ethyne via the Sonogashira reaction were established. Condensation between the 1-indanone and the ethyny1 derivatives produced the benzannulated enediynyl propargylic alcohol. Chlorinated P AHs as potential precursors leading to the bowlshpaed Cz1H12 hydrocarbon have been successfully synthesized.

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