Clay, Matthew D2013-11-082013-11-0820062006Source: Dissertation Abstracts International, Volume: 67-10, Section: B, page: 5751.http://hdl.handle.net/10393/29344http://dx.doi.org/10.20381/ruor-12904This thesis is composed of three sections and describes our work towards the synthesis of three molecules: Desogestrel, the first acetylenic allenophane, and Buckminsterfullerene. Section A details a tether-controlled diene-transmissive intramolecular Diels-Alder reaction approach to the oral contraceptive progestin Desogestrel. Using our indium-mediated gamma-pentadienylation chemistry as a key step, we synthesized tetraenes 92 and 68. Unfortunately, the intramolecular Diels-Alder reaction of these tetraenes resulted in formation of three isomers, bicyclo[4.3.0]nonenes 96 and 97, and the unusual bicyclo[3.3.1]nonene 99. Attempts to improve the selectivity were unsuccessful and precluded further pursuit of the synthesis. Section B of this thesis describes our design and asymmetric synthesis of the first acetylenic allenophane (308). This molecule represented a new class of cyclophane, and illustrative of the current interest in this type of molecule, several additional examples have since been reported, as well as an independent highlight in Angewandte Chemie. To complete our asymmetric synthesis, we developed a novel method of synthesizing tertiary propargyl alcohols (e.g., 299) in very good yield and enantioselectivity using a Sharpless asymmetric epoxidation as a key step. In contrast to the few procedures available for the asymmetric synthesis of tertiary propargyl alcohols, our protocol could be completed in roughly half the time, did not require the rigorous exclusion of oxygen or moisture, and did not require particularly specialized equipment. Section C describes our work towards a controlled laboratory synthesis of Buckminsterfullerene (C60) using hexakis[(Z)-enynyl]benzenes. We have developed several approaches to these molecules using trisubstituted benzene test substrates and have used these methods to construct hexasubstituted benzenes 417 and 418 from bromoaldehyde 399 . We are presently attempting to convert 418 to our cyclophane precursor to C60.270 p.enChemistry, Organic.Thesis