Date of Graduation
Eberly College of Arts and Sciences
Kung K Wang
Robert K Griffith
Jeffrey L Petersen
Brian V Popp
Bjorn C G Soderberg
Synthetic pathways for preparing furan-containing cycloparaphenylenes (CPPs) bearing 10, 12, and 15 aromatic units in the macrocyclic ring structures were developed. Several important steps used in these syntheses are the Suzuki--Miyaura cross-coupling reaction between the L-shaped building block and 2-furanylboronic ester the nickel-mediated homocoupling reaction to incorporate two and three 2,2'-bifuran-5,5'-diyl units into functionalized - and cycloparaphenylene (CPP) precursors. Oxidative aromatization of the precursors with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) under mild conditions led to the formation of fully aromatized furan-containing cycloparaphenylenes (CPPs).;The Diels--Alder reaction between the parent benzyne or 3,6-dimethoxybenzyne with furan-2,5-diyl units incorporated into functionalized CPP macrocycle followed by reductive deoxygenation of the Diels--Alder adducts with diiron nonacarbonyl, Fe2(CO)9 led to the formation of functionalized CPP macrocyclic precursors. Oxidative aromatization with DDQ produced functionalized cycloparaphenylenes bearing four evenly spaced biphenyl and naphthyl units. Additionally, a synthetic pathway for preparing a functionalized CPP has been developed. TetrahydroCPP was used to investigate the effect of macrocyclic ring size on the reaction rate of oxidative aromatization with DDQ.;Finally, a synthetic pathway for the construction of fused molecular nanohoops bearing two macrocyclic rings with different ring sizes by using two different 1,3-butadienes for the Diels--Alder reactions with 1,4-benzoquinone has been developed. The key intermediate in this strategy involves having four phenyl groups in cis position to one another after the second Diels--Alder reaction. This intermediate led to the formation of a fused carbon nanohoop bearing a tetrahydrocycloparaphenylene (4HCPP) fused to a 4HCPP and a macrocycle bearing a 4HCPP fused to a CPP inserted with two 2,2'-bithiophene-5,5'-diyl units.
Farajidizaji, Behzad, "Syntheses of Functionalized Cycloparaphenylenes, Furan-Containing Cycloparaphenylenes, and Related Thiophene-Containing Fused Carbon Nanohoop" (2017). Graduate Theses, Dissertations, and Problem Reports. 5576.