| In the field of supramolecular chemistry, structures that can bind guests are of significant interest. In the work presented herein, studies toward the synthesis of macromolecular host molecules are documented.; Part one deals with studies toward the synthesis of a modifiable cage compound, with the possibility of water solubility, to complement ongoing research efforts within the Warmuth group.; Synthesis of the modifiable hemicarceplex, 34,47-(Epoxybutanoxy)-20,24:57,61-dimetheno-2,25:17,29-dimetheno-3,51,16,30-(methynoxybutanoxymethyno)-1 H,18H,26H,28H,53 H55H-bis[1,3]benzodioxocino-[9',10 ':17,18;10″,9″:25,26][1,3,6,11,14,16,19,24]octaoxacyclohaxacosino[4,5-j:13,12-j ']bis[1,3]benzodioxocin, 8,9,10,11,39,40,41,42-Octahydro-1,18,26,28,53,55,63,80-octakis(3-butenyl)-, N-Methylpyrollidinone complex, (1.15) was accomplished, starting from condensation of resorcinol with 4-pentenal.{09}The initial condensation reaction between resorcinol and 4-pentenal gave unpredictable results, to which a discussion is provided. However, the synthetic intermediate leading toward 1.15, 2,8,14,20-Tetrakis(3-butenyl)-pentacyclo-[19.3.1.1 3,7,19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13 (27),-15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octol, was produced in moderate yield on a large scale.; Modification of the reported procedures developed by D. J. Cram and coworkers gave 1,21,23,25-Tetrakis(3-butenyl)-2,20;3,19-dimetheno-1H,21 H,-23H,25Hbis[1,3]-dioxocino[5,4- i:5',4'-i ']benzo[ 1,2-d:5,4-d']bis[ 1,3]benzodioxocin-7,11,15,28-tetrol, which was synthesized in three steps from resorcinol, which is one step less than previously reported. Initial studies upon protocavitand, 1,21,23,25-Tetrakis(3-butenyl)-2,20;3,19-dimetheno-1 H,21H,23H25H-bis[1,3]-dioxocino[5,4- i:5',4'-i ']benzo(1,2-d:5,4-d']bis[1,3]benzodioxocin, showed that epoxidation, cis-hydroxylation and subsequent oxidative cleavage of the pendant double bonds were all possible, showing the adaptability of the system. This adaptability was then tested on the more elaborate hemicarceplex.; Part two deals with a continuation of work developed within the Hua group, focused on the formation of a macropolycyclic beltene derivative, via a series of Diels-Alder reactions.; It is hypothesized that a properly functionalized beltene derivative could self assemble in solution, or possibly with the help of a rod-like guest, to give a cylindrical, tube like assembly that may help us in the understanding of ion channel behavior.; Synthesis of the key intermediate, 7,14-bis-(tert-butyldimethylsilyloxy)-2,3,9,10-tetrakis-hydroxymethyl-1,2,3,4,4a,5,6,7,7a,8,9,10,11,11a,12,13,14,14a-octadecahydro-6,13-[1,2]benzenopentacene-5,12-diol was optimized, by modifying some reactions developed by previous researchers within the Hua group.{09}Formation of the two key important intermediates, 7,14-bis-( tert-butyldimethylsilyloxy)-2,3,9,10-tetramethylene-1,4,4a,5,6,7,7a,8,11,11a,12,13,14,14a-tetradecahydro-6,13-[ 1,2]benzenopentacene-5,12-diol (2.32) and 5,7,12,14-tetrahydroxy-2,3,9,10-tetramethylene-1,4,4a,5,6,7,7a,8,11,11a,12,13,14,14a-tetradecahydro-6,13-[1,2]benzenopentacene (2.43) were also completed via a four fold selenoxide elimination reaction and subsequent deprotection for the latter compound. Further Diels-Alder reactions were investigated for these compounds and the results are discussed.; Finally, a targeted alternative pathway toward the synthesis of a beltene derivative through 2-(tert-butyldimethylsilyloxy)methyl-5,12-bis( tert-butyldimethylsilyloxy)-methyl-3,9,10-trishydroxymethyl-1,4,4a,5,6,7,7a,8,11,11 a,12,13,14,14a-tetradecahydro-6,13-[1,2]-benzenopentacene-7,14-diol was investigated and the results discussed herein. |
