| Attempts to construct robust three-dimensional, mostly carbon, covalent networks are reported. The strategy used to construct such networks involves monomer synthesis, self-assembly of monomers via hydrogen bonding, and covalent crosslinking. The syntheses of monomers are described, as well as attempts to crystallize these monomers in order to achieve a three-dimensional hydrogen-bonded network.; The synthesis of the racemic azaspirobicyclic core structure of halichlorine, a marine alkaloid that selectively inhibits VCAM-1 expression, is also reported. The key step of this route achieves the quaternary carbon found in halichlorine which involves a tandem Michael-1,5 C-H insertion sequence. A highly reactive alkynyl(aryl)iodonium salt is combined with a soft nucleophile to afford an alkylidene carbene, which undergoes subsequent 1,5 C-H insertion. |
